DE10315212A1 - Mixtures of alkoxylated alcohols, thiols or amines with water, for use e.g. in detergent or cleaning compositions, also containing water-soluble polymer having polar functions to eliminate turbidity - Google Patents

Abstract

A mixture comprises: (A) mono- or polyfunctional 2-24C alcohol, thiol or amine, alkoxylated with 1-30 ethylene oxide units and 0-3 3-10C alkylene oxide units; (B) water; and (C) water-soluble polymers having repeating units containing, optionally in salt form, hydroxy, carboxy, amine, amide, nitrogen-containing heterocyclyl, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate and/or phosphate groups. An independent claim is included for the preparation of (I) by mixing (A) - (C), where (C) is added before, during or after the alkoxylation reaction for the preparation of (A).

Description

The The invention relates to mixtures of alkoxylates, water and water-soluble Polymers, processes for their preparation, their use in laundry or cleaning agents or in the chemical-technical industry and methods for reducing the haze of aqueous alkoxylation products as well as the use of certain water-soluble polymers as additives to such alkoxylates to reduce turbidity in the production of aqueous Mixtures.

It is known from the literature that double metal cyanide compounds (DMC compounds) can be used as catalysts for the reaction of starter molecules with active hydrogen, such as alcohols, thiols or amines, with alkylene oxides, for example in a polymerization reaction. The ring-opening polymerization of alkylene oxides with DMC is for example in EP-B 0 892 002 and EP-A 0 755 716 described. DMC compounds or DMC catalysts have a high activity in the polymerization of alkylene oxides.

method for the alkoxylation of aliphatic alcohols and the obtained Alkoxylates are known in principle from the prior art. such Alkoxylates of aliphatic alcohols are used on a large scale used as surfactants, emulsifiers or foam attenuators. The wetting and Emulsifier properties depend strongly depends on the type of alcohol and the type and amount of alkoxide adducts from.

WHERE 94/11330 relates to alkoxylates of 2-propylheptanol and their use. When producing the alkoxylates, 2-propylheptanol is initially used 1 to 6 moles of propylene oxide and then 1 to 10 moles of ethylene oxide implemented as a catalyst in the presence of alkali metal hydroxides.

The alkoxylates obtained by the processes described above are usually in aqueous Systems sold and supplied to the applications. It has now been found that this watery Systems are not always clear solutions, but sometimes cloudiness demonstrate. This effect occurs particularly with alkoxylates that were alkoxylated under DMC catalysis. The cloudiness is not in all areas of application acceptable, so there is a demand for water-clear aqueous alkoxide mixtures consists.

task the present invention is the provision of aqueous Mixtures of alkylene oxides that are clear to the human eye appear and avoid the disadvantages of the known mixtures. moreover is to provide a method for reducing the turbidity of such mixtures become.

• a) monofunktionellen oder polyfunktionellen C₂_₂₄-Alkoholen, -Thiolen oder -Aminen, die im Mittel mit 1 bis 30 Ethylenoxideinheiten und 0 bis 3 C_3–10-Alkylenoxideinheiten alkoxyliert sind, als Komponente A,
• b) Wasser als Komponente B und
• c) wasserlöslichen Polymeren, die Wiederholeinheiten mit mindestens einer der folgenden funktionellen polaren Gruppen, gegebenenfalls in Salzform, aufweisen: Hydroxyl, Carboxyl, Amin, Amid, N-heterocyclische Gruppen, Thiol, Sulfonat, Sulfinat, Sulfat, Phosphonat, Phosphinat, Phosphat, als Komponente C.

The object is achieved by a mixture of

• a) monofunctional or polyfunctional C ₂ _ ₂₄ alcohols, thiols or amines, which are alkoxylated on average with 1 to 30 ethylene oxide units and 0 to 3 C ₃ -10 alkylene oxide units, as component A,
• b) water as component B and
• c) water-soluble polymers which have repeat units with at least one of the following functional polar groups, optionally in salt form: hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate, phosphate, as Component C.

• a) monofunktionellen oder polyfunktionellen C₂_₂₄-Alkoholen, -Thiolen oder -Aminen, die im Mittel mit 1 bis 30 Ethylenoxideinheiten oder 0 bis 3 C_3–10-Alkylenoxideinheiten alkoxyliert sind, als Komponente A,
• b) Wasser als Komponente B, durch Zusetzen von
• c) wasserlöslichen Polymeren, die Wiederholeinheiten mit mindestens einer der folgenden funktionellen polaren Gruppen, gegebenenfalls in Salzform, aufweisen: Hydroxyl, Carboxyl, Amin, Amid, N-heterocyclische Gruppen, Thiol, Sulfonat, Sulfinat, Sulfat, Phosphonat, Phosphinat, Phosphat, als Komponente C

zu den Gemischen.The object is also achieved by a process for reducing the turbidity of mixtures

• a) monofunctional or polyfunctional C ₂ _ ₂₄ alcohols, thiols or amines, which are alkoxylated on average with 1 to 30 ethylene oxide units or 0 to 3 C ₃ -10 alkylene oxide units, as component A,
• b) water as component B, by adding
• c) water-soluble polymers which have repeat units with at least one of the following functional polar groups, optionally in salt form: hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate, phosphate, as Component C

to the mixtures.

The object is further achieved by using water-soluble polymers which have repeating units with at least one of the following functional polar groups, optionally in salt form:
Hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate, phosphate, as component C,
as an additive to monofunctional or polyfunctional C ₂ _ ₂₄ alcohols, thiols or amines which are alkoxylated on average with 1 to 30 ethylene oxide units or 0 to 3 C ₃ -10 alkylene oxide units, as component A,
to reduce the turbidity during the preparation of aqueous mixtures of component A.

The mixtures according to the invention can preferably be used in washing or cleaning agents or used in the chemical-technical industry.

It was found according to the invention that by adding water-soluble Polymers that have the repeating units mentioned with functional have polar groups, cloudiness in aqueous alkoxylate mixtures can fix.

In particular Alkanol alkoxylates produced by double metal cyanide-catalyzed reaction can thus according to the invention in a stable and clear watery Wording to be transferred. The possible opacities should generally be avoided for purely visual reasons.

Without to be bound by this theory it seems possible that especially in DMC-catalyzed alkoxylation in low Amounts of high molecular weight alkoxylates are formed in the subsequent formulation in water to cloudiness to lead. By adding the water-soluble polymers Component C can remove this turbidity become.

The use according to the invention of the polymer component C to dissolve the turbidity in aqueous systems of the alkoxylation product component A differs from the known use of functional polymers as complex ligands in DMC catalysts. Corresponding DMC catalysts which contain functional polymers as complex ligands are, for example, in DE-A 199 53 546 , WO 01/04180, WO 99/19063 and US 5,714,428 described.

In the mixtures according to the invention are preferably 60 to 95% by weight of component A, 5 to 40 % By weight of component B and 0.001 to 1% by weight of component C before, based on the total weight of components A and B, the 100th Wt .-% results.

Especially is preferably here the proportion of component A 70 to 90 wt .-%, especially 75 to 85% by weight. For example the proportion of component A is about 80% by weight.

Corresponding is the proportion of component B is particularly preferably 10 to 30% by weight, particularly preferably 15 to 25% by weight, for example 20% by weight.

The Proportion of component C, based on the total weight of the components A and B particularly preferably 0.01 to 0.5% by weight, in particular 0.01 to 0.1 Wt .-%.

in the Episodes will follow first the components A, B and C closer explained.

component A

As component A monofunctional or polyfunctional C _{2- 24} alcohols, thiols or amines used, which are alkoxylated _3-10 alkylene oxide with an average of from 1 to 30 ethylene oxide units and 0 to 3 C. In the case of polyfunctional compounds, there are preferably 2 to 8, particularly preferably 2 to 6, in particular 2 to 4, functional groups. These are alcohols, thiols or amines, particularly preferably alcohols or thiols, in particular alcohols. The compounds have 2 to 24 carbon atoms, preferably 6 to 18 carbon atoms, in particular 8 to 15 carbon atoms. It is particularly preferably aliphatic compounds which can be linear, branched or partially branched, or alkylphenols, for example (C _6-12 -alkyl) phenols.

Particularly preferably, component A is based on monofunctional or polyfunctional C _{2- 24} alkanols. The alkanols are preferably linear or branched. In particular, monofunctional alkanols with 6 to 18 carbon atoms are used, particularly preferably alkanols with 8 to 15 carbon atoms, such as tridecanol or propylheptanol.

Alcohols suitable according to the invention are, for example, octanol, 2-ethylhexanol, nonanol, decanol, undekanol, dodekanol, 2-butyloctanol, tridekanol, tetradekanol, pentadekanol, iso-octanol, iso-nonanol, iso-decanol, iso-undekanol, iso-dodekanol, iso -Tridekanol, iso-tetradekanol, iso-pentadekanol, preferably iso-decanol, 2-propylheptanol, tridekanol, iso-tridekanol or mixtures thereof as well as mixtures of C _13-15 alcohols or mixtures of 2-propylheptanol with structurally isomeric C ₁₀ alcohols.

For example may be the alcohols used according to the invention Guerbet alcohols or structurally related alcohols, in particular ethylhexanol, Propylheptanol, butyloctanol.

According to the invention, the alcohols used as starter compound can also be mixtures of different isomers. For example, propylheptanol can be obtained starting from valeraldehyde by aldol condensation and subsequent hydrogenation. Valeraldehyde and the corresponding isomers are prepared by hydroformylation of butene, for example in US 4,287,370 ; Beilstein E IV 1, 32 68, Ullmanns Encyclopedia of Industrial Chemistry, 5th edition, volume A1, pages 323 and 328 f. The following aldol condensation is described for example in US 5,434,313 and Römpp, Chemie Lexikon, 9th edition, keyword "Aldol addition" page 91. The hydrogenation of the aldol condensation product It follows general hydrogenation conditions.

Of Furthermore, 2-propylheptanol can be condensed by 1-pentanol (as a mixture of the corresponding methylbutanols-1) in the presence of KOH at elevated Temperatures are established, see for example Marcel Guerbet, C.R. Acad Sci Paris 128, 511, 1002 (1899). Furthermore, on Römpp, chemistry Lexicon, 9th edition, Georg Thieme Verlag Stuttgart, and those there quotations as well as Tetrahedron, Vol. 23, pages 1723 to 1733, to point.

Secondary alcohols or mixtures are also suitable. These can be obtained, for example, by adding ketones to aldehydes with subsequent hydrogenation, as in the DE-A 100 35 617 described. Methyl ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone are preferred. Paraffin oxidation products which are produced, for example, by Bashkirov oxidation are also suitable. Here are products of C ₁₁ - C ₁₆ paraffin mixtures, especially products of C _13-14 paraffin mixtures, are preferred. Suitable alcohols are also e.g. B. secondary alcohols obtained by adding water to olefins or by radical or other oxidation of olefins.

The monofunctional or polyfunctional compounds are alkoxylated on average with 1 to 30 ethylene oxide units and 0 to 3 C _3-10 alkylene oxide units. There are preferably on average 2 to 25, particularly preferably 2 to 20, especially 2 to 18 ethylene oxide units and preferably 0 to 2, in particular 0 to 1.5, C _3-10 alkylene oxide units. If these higher alkylene oxide units are present, their proportion is on average preferably 0.1 to 3, particularly preferably 0.5 to 2, in particular 1 to 1.5.

Examples of suitable C _3-10 alkylene oxides, preferably C _4-10 alkylene oxides, are propylene oxide, butylene oxide and pentylene oxide and mixtures thereof. Butylene oxide can be selected from 1-butylene oxide, cis-2-butylene oxide, trans-2-butylene oxide and isobutylene oxide.

The Alkylene oxide mixtures preferably have an ethylene oxide content of more than 50% by weight, particularly preferably of more than 75% by weight, in particular of more than 95% by weight, for example of more than 99% by weight. In a preferred embodiment, according to the invention Ethylene oxide no further alkylene oxide used.

at The alkoxylation results in a distribution of the degree of alkoxylation on. The numerical values given are therefore mean values.

The alkoxylation can be carried out under any suitable conditions. For example, the alkoxylation can be carried out in the presence of alkali metal hydroxides as a catalyst. Such a method is described in WO 94/11330. The alkanols are preferably alkoxylated with DMC catalysis. Corresponding processes and catalysts are, for example, in EP-B 0 892 002 . EP-A 0 755 716 described. The reaction is preferably carried out at temperatures in the range from 80 to 190.degree.

The preferred alkanol alkoxylates used according to the invention as component A are nonionic surfactants. Their production by alkoxylation under DMC catalysis has a number of application advantages:
On the one hand, a narrow molecular weight distribution is achieved. Furthermore, there is only a very low residual alcohol content in the product, so that the inherent odor of the alkoxylates is reduced. There is no need to remove the residual alcohol. Furthermore, the use of only small amounts of catalyst is necessary. The catalyst can thus remain in the product. Removal of the catalyst, as is usually necessary in KOH catalysis, can be omitted.

Therefore the alkoxylates of component A are preferably by DMC catalysis manufactured. A particularly preferred alkoxylate is derived from 2-propylheptanol from that first reacted with 1 mol of propylene oxide and then with 4 to 6 mol of ethylene oxide has been.

• – k eine gebrochene oder ganze Zahl größer oder gleich Null ist, und
• – P ein organischer Zusatzstoff ist,

a, b, c, d, g und n so ausgewählt sind, dass die Elektroneutralität der Verbindung (I) gewährleistet ist, wobei c = 0 sein kann,
e die Anzahl der Ligandenmoleküle eine gebrochenen oder ganze Zahl größer 0 oder 0 ist,
f und h unabhängig voneinander eine gebrochene oder ganze Zahl größer 0 oder 0 sind.The process according to the invention for producing an alkoxylate is carried out in particular in the presence of a double metal cyanide compound of the general formula I as a catalyst: M ¹ _a [M ² (CN) _b (A) _c ] _d ∙ fM ¹ _g X _n ∙ h (H ₂ O) ∙ eL ∙ kP (I), in the
M ¹ at least one metal ion selected from the group consisting of Zn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ³⁺ , Ni ²⁺ , Mn ²⁺ , Co ²⁺ , Sn ²⁺ , Pb ²⁺ , Mo ^{4 +} , Mo ⁶⁺ , Al ³⁺ , V ⁴⁺ , V ⁵⁺ , Sr ²⁺ , W ⁴⁺ , W ⁶⁺ , Cr ²⁺ , Cr ³⁺ , Cd ²⁺ , Hg ²⁺ , Pd ²⁺ , Pt ²⁺ , V ²⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Cu ²⁺ , La ³⁺ , Ce ³⁺ , Ce ⁴⁺ , Eu ³⁺ , Ti ³⁺ , Ti ⁴⁺ , Ag ⁺ , Rh ²⁺ , Rh ³⁺ , Ru ²⁺ , Ru ³⁺ is,
M ² at least one metal ion selected from the group consisting of Fe ²⁺ , Fe ³⁺ , Co ²⁺ Co ³⁺ , Mn ²⁺ , Mn ³⁺ , V ⁴⁺ , V ⁵⁺ , Cr ²⁺ , Cr ³⁺ , Rh ³⁺ , Ru ²⁺ , Ir ³⁺
A and X are independently an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, hydrogen sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate or hydrogen carbonate,
L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes the, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, primary, secondary and tertiary amines, ligands with pyridine nitrogen, nitriles, sulfides, phosphides, phosphites, phosphines, phosphonates and phosphates,

• - k is a fractional or whole number greater than or equal to zero, and
• - P is an organic additive,

a, b, c, d, g and n are selected so that the electroneutrality of the compound (I) is ensured, where c = 0,
e the number of ligand molecules is a fractional or an integer greater than 0 or 0,
f and h are independently a fractional or whole number greater than 0 or 0.

As Organic additives P are mentioned: polyether, polyester, Polycarbonates, polyalkylene glycol sorbitan esters, polyakylene glycol glycidyl ethers, Polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, Polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, Polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, Poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, Poly (4-vinylphenol), poly (acrylic acid-co-styrene), Oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymers, Hydroxyethyl cellulose, polyacetates, ionic surface and surface active Compounds, bile acid or their salts, esters or amides, carboxylic acid esters of polyhydric alcohols and glycosides.

This Catalysts can be crystalline or amorphous. For if k is zero, crystalline double metal cyanide compounds prefers. In the event that k is greater than zero is both crystalline, semi-crystalline and substantial amorphous catalysts preferred.

Of there are various preferred catalysts Embodiments. A preferred embodiment are catalysts of the formula (I) in which k is greater than zero is. The preferred catalyst then contains at least one double metal cyanide compound, at least an organic ligand and at least one organic additive P.

at another preferred embodiment k is zero, optionally e is also zero and X is exclusively a Carboxylate, preferably formate, acetate and propionate. Such catalysts are described in WO 99/16775. In this embodiment crystalline double metal cyanide catalysts are preferred. Further double metal cyanide catalysts are preferred, as in WO 00/74845 described, which are crystalline and platelet-shaped.

The The modified catalysts are produced by association a metal salt solution with a cyanometalate solution, which optionally have both an organic ligand L and an organic one May contain additive P. Subsequently become the organic ligand and optionally the organic additive added. In a preferred embodiment of the catalyst preparation will first an inactive double metal cyanide phase is produced and then by recrystallization converted into an active double metal cyanide phase, as in PCT / EP01 / 01893 described.

In another preferred embodiment of the catalysts, f, e and k are not equal to zero. These are double metal cyanide catalysts which contain a water-miscible organic ligand (generally in amounts of 0.5 to 30% by weight) and an organic additive (generally in amounts of 5 to 80% by weight) such as described in WO 98/06312. The catalysts can be produced either with vigorous stirring (24,000 rpm with Turrax) or with stirring as in the US 5,158,922 described.

In particular are suitable as a catalyst for the alkoxylation of double metal cyanide compounds containing zinc, cobalt or Contain iron or two of them. For example, is particularly suitable Berlin blue.

Prefers crystalline DMC compounds are used. In a preferred one embodiment becomes a crystalline Zn-Co type DMC compound as a catalyst used, which contains zinc acetate as a further metal salt component. Such connections crystallize in a monoclinic structure and have a platelet-shaped habit on. Such compounds are described, for example, in WO 00/74845 or the PCT / EP01 / 01893.

As In principle, suitable DMC compounds can be used on all of the Types known to those skilled in the art can be produced. For example, the DMC connections through direct precipitation, “incipient wetness "method, by producing a precursor phase and subsequent recrystallization getting produced.

The DMC connections can be used as a powder, paste or suspension or to form a moldings be deformed, in moldings, foams or the like be introduced or applied to moldings, foams or the like.

The catalyst concentration used for alkoxylation on the final quantity framework is typically less than 2000 ppm (i.e. mg catalyst per kg of product), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, particularly preferably less than 25 ppm.

In a preferred embodiment The present invention relates to a method in which the double metal cyanide compound in an amount of 100 ppm or less, based on the final quantity structure becomes.

• (1) M¹ ist ausgewählt aus der Gruppe Zn²⁺, Fe²⁺, Fe³⁺, Co³⁺, Ni²⁺, Mn²⁺, Co²⁺,
• (2) M² ist ausgewählt aus der Gruppe Fe²⁺, Fe³⁺, Co³⁺.

oder besonders bevorzugt ein Verfahren, wobei M¹ Zn²⁺ ist und M² Co³⁺.In further embodiments, the present invention relates to a method, wherein at least one of the following properties is fulfilled:

• (1) M ¹ is selected from the group Zn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ³⁺ , Ni ²⁺ , Mn ²⁺ , Co ²⁺ ,
• (2) M ² is selected from the group Fe ²⁺ , Fe ³⁺ , Co ³⁺ .

or particularly preferably a process in which M ^{1 is} Zn ²⁺ and M ² Co ³⁺ .

at In the method, for example, the reaction vessel can first be equipped with a Suspension of alcohol and DMC catalyst can be filled. Then you can the catalyst by separating water, e.g. B. by heating and / or evacuation of the reaction vessel can be activated.

Then will the reaction mixture advantageously at the reaction temperature warmed and a nitrogen blanket is set. In the further course of the procedure For example, a starting amount of ethylene oxide is metered in. To as the reaction starts, further ethylene oxide is metered in, the reaction mixture is stirred, until all ethylene oxide has reacted. The reaction mixture can if necessary, be worked up further.

The Pressure changes yourself during the reaction. After a possible one initial Pressure drop when the reaction starts, the pressure increases in the course the reaction since the level rises in the reactor and the gas mixture is compressed. It is according to the invention preferred that the total pressure, in particular the sum of the inert gas partial pressure and ethylene oxide partial pressure, not more than 20 bar in the course of the reaction, for example not over 11 bar, preferably not over 6 bar, especially not over 3.5 bar increases.

The inventive method is carried out at temperatures from 80 to 190 ° C.

component B

As Component B is water. The water can contain salts or additives in usual Contain quantities that do not or do not have the chemical character significantly affect. Salts can for example in amounts of at most 5% by weight, in particular at most 3% by weight are present. Technically pure water is preferably used.

component C

As component C, water-soluble polymers are used which have repeat units with at least one of the following functional polar groups, optionally in salt form:
Hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate, phosphate.

in the Within the scope of the present invention, such polymers are described as water-soluble, which at least 1% soluble in water are. This means that 1 g of polymer dissolves in 99 g of water. preferred water-soluble Polymers are at least 5% soluble in water.

The used according to the invention water-soluble Polymers have number average molecular weights of, for example 100 to 20,000, preferably 1,000 to 10,000, in particular 3,000 up to 5,000.

The water-soluble Polymers preferably show dispersing, emulsifying and / or surface-active Characteristics. The polymers preferably have repeat units with at least one of the following functional polar groups: Acrylic acid groups, Maleic anhydride groups, Naphthalene sulfonic acid groups, Ethyleneimine groups.

Examples suitable polymers are acrylic acid-maleic anhydride copolymers, Naphthalene sulfonic acid-formaldehyde condensates, each in the H form or in the form of salts, in particular alkali salts, especially sodium salts, may be present, polyethyleneimines and Ethoxylates thereof.

suitable Polymers are known to the person skilled in the art and can be obtained by simple experiments be determined.

The dispersing, emulsifying and / or surface-active properties are expressed in particular in that when the polymers are added to the components A and B clear solutions be preserved.

The Polymers are preferably used in amounts of 0.001 to 1% by weight, especially preferably 0.01 to 0.5% by weight, in particular 0.01 to 0.1% by weight, based on the sum of components A and B used.

Next the repeating units with the specified functional polar Groups often contain the polymers Basic comonomer building blocks that have no functional polar groups exhibit. These other basic building blocks are chosen so that they the water solubility of the polymers not to an extent affect which they are for the application according to the invention would make unsuitable. Examples of suitable comonomer repeat units can be found for example of olefins, styrene, acrylonitrile, (meth) acrylic acid esters and the like Derive basic building blocks.

The The amount of polymer used can be, for example, 500 to 2000 ppm.

The Water-soluble polymers used as component C can already in the manufacture of component A, i.e. in the alkoxylation, provided they are inert under the alkoxylation conditions. This means that the polymers do not participate in the alkoxylation reaction participate or not or only alkoxylated to a small extent become. Unless the water-soluble polymers would be significantly changed under the alkoxylation conditions the addition only after production of the finished component A.

Without to be bound by this theory it can be assumed that the water soluble Polymers as dispersants for the the cloudiness causing mixture components act. Becomes a cloudiness understood as such turbidity in the context of the present invention, the for the human eye is recognizable. Such, for human Opacity visible to the eye can by liquid or solid substances that are not completely compatible with the watery Mix system. The particle size of the remaining Liquid droplets or Solids are such that they are perceived by the human eye becomes. A solution or a watery one System is accordingly described as clear, provided it is human Eye appears as clear. This is especially the case when droplets of liquid or Solids in water System or the watery solution are present, however, are so small that they are none for the human Eye-recognizable cloudiness to lead.

The The invention also relates to a method for producing the above mixtures described by mixing components A, B and C, where, as already stated above, component C also, while or added after the alkoxylation to produce component A. can. The addition of component C is directed as indicated according to the chemical structure of the polymer.

The Adding the water-soluble Component C polymers generally take place at temperatures from 0 to 95 ° C, preferably 10 to 70 ° C, particularly preferably 20 to 55 ° C.

the It is known to the person skilled in the art that contamination occurs in double metal cyanide catalysis Amines, alkali hydroxides or good complex ligands can be excluded. In these cases should the addition of appropriate polymers therefore only after the alkoxylation.

The mixtures according to the invention can in Detergents or cleaning agents or in the chemical-technical industry be used. usual Areas of application of the mixtures are use as an emulsifier, Foam regulator, wetting agent for hard Surfaces, Thickener for aqueous Systems, heat transfer fluids and similar Applications. In these applications, the alkoxylates of the component A usually in an aqueous System used with an active ingredient content of 60 to 95 wt .-%. It is now possible optically to provide appealing clear blends that are easy to use can be used in all areas of application.

Further Areas of application are known to the person skilled in the art.

• a) monofunktionellen oder polyfunktionellen C₂_₂₄-Alkoholen, -Thiolen oder -Aminen, die im Mittel mit 1 bis 30 Ethylenoxideinheiten oder 0 bis 3 C_3–10-Alkylenoxideinheiten alkoxyliert sind, als Komponente A,
• b) Wasser als Komponente B

durch Zusetzen von

• c) wasserlöslichen Polymeren, die Wiederholeinheiten mit mindestens einer der folgenden funktionellen polaren Gruppen, gegebenenfalls in Salzform, aufweisen: Hydroxyl, Carboxyl, Amin, Amid, N-heterocyclische Gruppen, Thiol, Sulfonat, Sulfinat, Sulfat, Phosphonat, Phosphinat, Phosphat, als Komponente C

zu den Gemischen.The invention further relates to a method for reducing the turbidity of mixtures

• a) monofunctional or polyfunctional C ₂ _ ₂₄ alcohols, thiols or amines, which are alkoxylated on average with 1 to 30 ethylene oxide units or 0 to 3 C ₃ -10 alkylene oxide units, as component A,
• b) water as component B

by adding

• c) water-soluble polymers which have repeat units with at least one of the following functional polar groups, optionally in salt form: hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate, phosphate, as Component C

to the mixtures.

The invention further relates to the use of water-soluble polymers, the repeating units with at least one of the following functional polar groups, optionally in salt form, have: hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate, phosphate, as component C, as an additive to monofunctional or polyfunctional C _2-24 alcohols -thiols or Amines, which are alkoxylated on average with 1 to 30 ethylene oxide units or 0 to 3 C _3-10 alkylene oxide units, as component A, to reduce the turbidity in the preparation of aqueous mixtures of component A.

The The invention is illustrated by the following examples:

example 1

As Component A was 2-propylheptanol, reacted with 1.2 mol first Propylene oxide and then 6 mol ethylene oxide, each determined as mol / mol, used. 100 g of this component A were mixed with 25 g of water, being a cloudy mixture was obtained. Then 400 ppm was one with maleic anhydride modified polyacrylic acid added as a polycarboxylate. The mixture was shaken vigorously and optically assessed after a waiting period. The wording was clear.

Example 2

As Component A was 2-propylheptanol, initially reacted with 1,2 mol of propylene oxide and then 5 mol of ethylene oxide. 100 g Component A was mixed with 400 ppm of the polycarboxylate from Example 1 offset. The mixture was cloudy. 25 g of water were added to the mixture. The mixture was strongly shaken and then left standing. The formulation obtained was water-clear.

Example 3

As Component A was 2-propylheptanol, reacted with 1.2 mol propylene oxide and then 5 mol or 6 mol of ethylene oxide are used. Each 100 g of this component A with 20 wt .-% water overnight to 60 ° C heated. Both formulations were cloudy. Then both formulations were each 500 ppm of the polycarboxylate added from Example 1. The two mixtures were each shaken vigorously and then left to stand. Both phrases were clear.

Determination of turbidity (turbidimeter)

The Systems examined were using a Hach turbidity meter (Ratio / XR turbidimeter). The measurement results provide dimensionless Numerical values and are about so-called NTU units (normal turbidity unit) specified.

Example 4

As Component A was 2-propylheptanol, reacted with 1.2 mol first Propylene oxide and then 5 mol of ethylene oxide. 100 g of Component A was mixed with 25 g of water. The mixture pointed a cloudiness of 11 turbidity units. After adding 500 ppm of the polycarboxylate from Example 1 reduced the cloudiness on 5 turbidity units.

At the Use of a 2-propylheptanol, first reacted with 1.2 mol propylene oxide and then 6 moles of ethylene oxide, the turbidity of 8 turbidity units before adding the additive to 3 turbidity units reduced after the additive addition. The finished formulations were included each for mixed in the ultrasonic bath for about 10 minutes.

At the Use of 2-propylheptanol, first reacted with 1.2 mol propylene oxide and then 4 moles of ethylene oxide as component A resulted for a mixture from 50 g of component A with 12.5 g of water a turbidity of 32 turbidity units. To The addition of 700 ppm of the polycarboxylate from Example 1 was reduced the cloudiness on 6 turbidity units.

Has been an appropriate amount instead of the polycarboxylate from Example 1 of a naphthalenesulfonic acid condensate used in the form of the sodium salt, there was a reduction the cloudiness on 16 turbidity units.

Claims (9)

Mixture of a) monofunctional or polyfunctional C ₂ _ ₂₄ alcohols, thiols or amines, which are alkoxylated on average with 1 to 30 ethylene oxide units and 0 to 3 C _3–10 alkylene oxide units, as component A, b) water as component B and c) water-soluble polymers which have repeat units with at least one of the following functional polar groups, optionally in salt form: hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate, phosphate , as component C. Mixture according to Claim 1, characterized in that 60 to 95% by weight of component A, 5 to 40% by weight of component B and 0.001 to 1% by weight of component C are present, based on the total weight of the com components A and B, which gives 100 wt .-%. Mixture according to claim 1 or 2, characterized in that component A is based on monofunctional or polyfunctional C _2-24 alkanols. Mixture according to claim 3, characterized in that the alkanols under DMC catalysis are alkoxylated. Mixture according to one of claims 1 to 4, characterized in that that it is a clear solution. Process for the preparation of mixtures according to a of claims 1 to 5 by mixing components A, B and C, also Component C before, during or added after the alkoxylation to produce component A. can be. Use of mixtures according to one of claims 1 to 5 in washing and cleaning agents or in the chemical-technical Industry. Process for reducing the turbidity of mixtures of a) monofunctional or polyfunctional _{C2-24 alcohols} , thiols or amines, which are alkoxylated on average with 1 to 30 ethylene oxide units or 0 to 3 C _3-10 alkylene oxide units, as component A b) water as component B, by adding c) water-soluble polymers which have repeating units with at least one of the following functional polar groups, optionally in salt form: hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, Sulfinate, sulfate, phosphonate, phosphinate, phosphate, as component C, to the mixtures. Use of water-soluble polymers which have repeat units with at least one of the following functional polar groups, optionally in salt form: hydroxyl, carboxyl, amine, amide, N-heterocyclic groups, thiol, sulfonate, sulfinate, sulfate, phosphonate, phosphinate, phosphate, as component C, as an additive to monofunctional or polyfunctional C _{2- 24} alcohols, -thiols or -amines which have been alkoxylated with an average of from 1 to 30 ethylene oxide units or 0 to 3 C _3-10 alkylene oxide units, as component A, for the reduction of Turbidity in the preparation of aqueous mixtures of component A.