EP1660551A1

EP1660551A1 - Foam regulating agent based on cationic urethane oligomers

Info

Publication number: EP1660551A1
Application number: EP04764548A
Authority: EP
Inventors: Son Nguyen-Kim; Ralf NÖRENBERG
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-08-27
Filing date: 2004-08-27
Publication date: 2006-05-31
Also published as: CN100523035C; WO2005021613A1; JP2007503495A; CN1842553A; JP4318719B2; CA2535067A1; BRPI0413415A; DE10339479A1; US20060263324A1; US7807725B2; MXPA06001682A

Abstract

The invention relates to a cationic poly(ether-urethane) consisting of a) at least one polyetherol, as constituent A; b) at least one tertiary diol containing amine or ammonium, as constituent B; c) at least one diisocyanate, as constituent C; d) and optionally at least one shortstopping agent, as constituent D; the cationic poly(ether-urethane) having an amine value of between 5 and 40. The invention also relates to a method for producing the inventive cationic poly(ether-urethanes), to compositions containing said cationic poly(ether-urethanes) and at least one anionic surfactant, to a method for foam regulation, especially for the suppression of foam or for defoaming, using at least one inventive cationic poly(ether-urethane), and to the use of said cationic poly(ether-urethane) for foam regulation, especially as a foam suppressing agent or a defoaming agent.

Description

Foam control agent based on cationic urethane oligomers

The present invention relates to cationic poly (ether urethanes), a process for their preparation, compositions comprising the cationic poly (ether urethanes) according to the invention and at least one anionic surfactant, a process for regulating foam, in particular for suppressing foam or for defoaming using at least one cationic poly (ether-urethane) according to the invention, the use of the cationic poly (ether-urethane) according to the invention for foam regulation, in particular as a foam suppressor or defoamer.

Among other things, surfactants (surface-active compounds) play an important role in numerous applications due to their property of enabling the miscibility of aqueous phases and oil phases. A known property of surfactant solutions is their tendency to generate foam, especially when the solutions are moved.

There are applications where foaming is undesirable, i.e. H. in these applications, reduction, suppression or elimination of foam is desirable. In washing machines, for example, detergent compositions which have only a low foaming are desirable. Other applications in which foaming is undesirable include coatings, where foaming can adversely affect the appearance of the coatings, machine bottle cleaning, and other applications, where foaming affects cleaning efficiency and / or causes water stains.

Defoamers commonly used for detergents are used, for example, as a coating on sodium carbonate particles. These materials are powders that can be dry mixed with various powder detergent formulations. Such defoamer materials are, for example, silicone-based defoamers on inorganic supports, which are used in powder detergents. While these conventional defoamers have some effectiveness in suppressing foam when used in conjunction with powder detergent compositions, they are not suitable for use in liquid detergent compositions. In liquid detergent compositions, soap is used as a defoamer in the prior art. The soap interacts with the ions of the hard water and forms insoluble particles that can suppress foam formation. The defoamer properties of soap are therefore dependent on the ions of the hard water, so that the use of soap as a defoamer when using soft water is not very successful. Furthermore, silicone-based defoamers have already been used in liquid systems, such as detergent compositions, dispersions, emulsions and cosmetics, but compatibility problems do arise.

In addition to these hydrophobic particles, there are other technologies. For example, hydrophobic surfactants, which form oil lenses in the foam lamella under conditions of use, defoam oil or fat particles, in particular silicone oils. P.R. offers an overview of the different defoamer technologies. Garrett in “Defoaming. Theory and Industrial Application ", P.R. Garrett (ed.), Surfactant Science Series 45, 1993, 1-117.

WO 01/76 729 relates to compositions comprising at least one anionic surfactant and at least one multifunctional polyetheramine which contains at least two amino groups per molecule and has a molecular weight of at least 1000, in which each amino group is a secondary or tertiary amino group. The multifunctional polyetheramine serves as a foam suppressant in these compositions.

The object of the present application is to provide novel compounds which are suitable as foam regulating agents, in particular as defoamers and / or foam suppressants in formulations which contain at least one anionic surfactant.

This object is achieved by a cationic poly (ether-urethane) composed of a) at least one polyetherol, as component A; b) at least one tertiary amine-containing or ammonium-containing diol, as component B; c) at least one diisocyanate as component C; d) optionally at least one stopper, as component D; wherein the cationic poly (ether-urethane) has an amine number from 5 to 40.

It has been found that certain cationic poly (ether-urethanes) are suitable as foam regulating agents, in particular as defoamers and / or foam suppressants, in compositions which contain at least one anionic surfactant.

For the purposes of the present application, defoamer is to be understood as a substance which is suitable for reducing or completely removing existing foam. Foam suppressant is to be understood as a substance which is suitable for at least partially or completely suppressing the formation of foam.

The cationic poly (ether-urethane) according to the invention has an amine number of 5 to 40, preferably 10 to 30, particularly preferably 10 to 25. The amine number was measured using the method described in DIN 16945.

The polyurethanes generally have a K value according to H. Fikentscher (determined in 0.1% by weight solutions in N-methyl-pyrrolidone at 25 ° C. and pH 7) of 15 to 40.

The glass transition temperature of the poly (ether-urethanes) according to the invention is generally <20 ° C., preferably <15 ° C., particularly preferably <5 ° C. The glass transition temperature was determined in accordance with ASTM D 3418.

In a preferred embodiment, the present application relates to a cationic poly (ether-urethane) containing a) 50 to 90% by weight, preferably 55 to 85% by weight, particularly preferably 60 to 80% by weight of component A, b ) 1 to 10% by weight, preferably 2 to 7% by weight, particularly preferably 2.5 to 5% by weight of component B, c) 9 to 25% by weight, preferably 14 to 23% by weight %, particularly preferably 17 to 21% by weight of component C, d) 0 to 15% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight of component D, the total sum of components A, B, C and optionally D 100 % By weight.

The cationic poly (ether-urethanes) according to the invention are generally readily alcohol- and water-soluble, or at least without the aid of emulsifiers, in alcohols and water, owing to their cationic groupings, especially when charges are present. Short-chain alcohols such as methanol, ethanol, isopropanol or n-propanol are particularly suitable as alcohols here. Furthermore, in a preferred embodiment, the cationic poly (ether-urethanes) according to the invention are soluble or dispersible in oils. Suitable oils are, for example, paraffin oils such as diesel oil and cosmetic oils such as essential oils.

For the use of the poly (ether-urethanes) according to the invention as foam regulating agents, in particular as defoamers and / or foam suppressors, the amine number of the poly (ether-urethanes) - and thus the charge density - is of crucial importance. The following was ascertained, without being bound to any mechanistic ideas possibly connected with the following statement: If the charge density is too high, the polymers precipitate together with the anionic surfactants. If the charge density is too low, the interaction of the poly (ether-urethanes) with the anionic surfactants is too low.

Component A

Suitable polyetherols are selected from the group consisting of poly (C ₃ - to C ₅ -) glycols, polytetrahydrofuran, mixtures of the aforementioned compounds and mixtures of at least one of the aforementioned compounds with polyethylene glycol. Poly (C ₃ - to C ₅ -) glycols are to be understood as meaning polyalkylene glycols whose alkylene groups are composed of three, four or five carbon atoms. Such polyalkylene glycols are polypropylene glycol, polybutylene glycol and polypentylene glycol. The suitable poly (C3 to C ₅ -) glycols generally have a molecular weight of 200 to 5000, preferably 450 to 3000, particularly preferably 500 to 1500, determined from the OH number according to DIN 53240. Suitable polytetrahydrofurans generally have a molecular weight of 250 to 3000, preferably 450 to 2000, particularly preferably 500 to 1200, determined from the OH number according to DIN 53240.

It is also possible to use mixed polyalkylene glycols as component A, which are obtained by polymerizing various alkylene oxides such as propylene oxide, butylene oxide, pentylene oxide and / or ethylene oxide. The alkylene oxide units can be randomly distributed in the polyalkylene glycol obtained or copolymerized in the form of blocks. Furthermore, copolymers of at least one alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide or pentylene oxide with THF are suitable as component A, the alkylene oxide and THF units being randomly distributed in the copolymer obtained or copolymerized in the form of blocks, which is preferred can. The proportion of the at least one alkylene oxide unit in the copolymer is preferably at most 30% by weight.

Polypropylene glycol and ethylene oxide / propylene oxide block copolymers are very particularly preferably used as component A. The proportion of ethylene oxide units in the ethylene oxide / propylene oxide block copolymers is preferably <40% by weight, particularly preferably <20% by weight.

The preparation of the polyalkylene glycols mentioned and of polytetrahydrofuran, the mixtures and copolymers mentioned above is known to the person skilled in the art.

Component B

Diols, aminoalcohols, diamines or triamines with at least one quaternary or protonated or protonatable amine nitrogen atom are suitable as component B. At least one compound of the general formulas I to VIII is preferably used

HO-R- (IV

1 R ^3b HO-RN / ^ ^"" λ NH (VR ⁴ HN-RNR-NHR ⁵ (VI

R HN-RN NH (VII R ⁴ HN-R ¹ -N NR-NHR ⁵ (VIII

in which R ¹ and R ^{2 are} alkylene, preferably C ₂ -C ₈ -alkylene, R ^3a , R ⁶ and R ⁷ , R ^{8 are} alkyl, aryl, alkylaryl or arylalkyl, preferably Cr to C ₄ -alkyl, phenyl or C ₇ - to Cι ₀ -phenylalkyl mean

R ⁴ and R ^{5 are} hydrogen or C to C - alkyl,

_R 3b is C to C ₁₈ alkyl, phenyl or C ₇ - to C ₀ -phenylalkyl, and X ^"means chloride, bromide, iodide, C to C ₄ alkyl sulfate or half the stoichiometric amount of sulfate.

Examples of C ₂ - to C ₈ -alkylene include 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 2,2-dimethyl-1, 3-propylene, 1, 2-propylene, 1, 2-butylene, 2,3-butylene, pentamethylene, hexamethylene, heptamethylene or octamethylene. D- to C ₄ -alkyl are understood to mean, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl, preferably methyl and ethyl. C ₇ - to Cio-phenylalkyl means, for example, benzyl, 2-phenylethyl, o-, m- and p-methylbenzyl, 3-phenylpropyl or 4-phenylbutyl, preferably benzyl and 2-phenylethyl. Examples of d- to cis-alkyl include methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec.-

Butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, the various isomers of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetra to understand decyl, pentadecyl, hexadecyl and octadecyl radicals. The C to Cιs alkyl radicals can be linear or branched.

Component B is preferably selected from the group consisting of at least one amine-containing or ammonium-containing diol of the formulas I to IV,

HO-R- (III)

X wherein the symbols have the meanings already mentioned above.

Compounds of the formula I are very particularly preferably used as component B, in which the radicals R ¹ , R ² and R ^3a and R ^{3b have} the meanings mentioned above. R ¹ and R ² are preferably C ₂ -C 5 -alkylene and R ^3a Cr to C-is-alkyl, particularly preferably d- to C ₄ -alkyl and R ^3b Cr to Ci8-alkyl, particularly preferably Cr to C ₄ -alkyl alkyl. Component B is very particularly preferably selected from the group consisting of diethanolamines, in particular methyldiethanolamine.

Component C

In principle, all diisocyanates are suitable as component C. Component C is preferably selected from the group consisting of C ₂ - to C ₈ -alkyl diisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate; C ₅ - to C1 ₀ - cycloalkylene diisocyanates such as 1,3-pentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclhexylene diisocyanate, isophorone diisocyanate; o-, m-, p-phenylene diisocyanate and (d- to C ₄ -alkyl) phenylene diisocyanates such as tolylene diisocyanate. Here, (d- to C ₄ -alkyl) phenylene diisocyanates are to be understood as phenylene diisocyanates whose phenylene group contains one or more, preferably adds a, d- to C ₄ -alkyl radical carries. Preferred diisocyanates are C ₂ to C ₈ alkylene diisocyanates, particularly preferably hexamethylene diisocyanate.

Component D

The cationic poly (ether-urethanes) according to the invention are distinguished by a relatively low molecular weight. In order to obtain such cationic poly (ether-urethanes) with a relatively low molecular weight, stoppers can be added as component D in the preparation of the cationic poly (ether-urethanes). Suitable stoppers are known to the person skilled in the art. Stoppers selected from the group consisting of monofunctional amines, monofunctional alcohols, water and monofunctional thiols are preferably used. Tertiary amine-containing diols such as dimethylaminoalkylamines are particularly preferably used, preference being given to C ₂ - to Cs-alkyl radicals, in particular dimethylaminopropylamine. Furthermore, dimethylethanolamine and monofunctional alcohols are preferably used as stoppers. However, it is also possible to obtain cationic poly (ether-urethanes) with a relatively low molecular weight without the addition of stoppers. Due to impurities present in the reaction mixture, in particular water, poly (ether-urethanes) with a relatively low molecular weight can be obtained without the addition of stoppers.

Production of poly (ether-urethanes)

The cationic poly (ether-urethanes) according to the invention are generally prepared by processes known to those skilled in the art. The cationic poly (ether-urethanes) according to the invention are preferably obtainable by reacting the diisocyanate (component C) reactants under an inert gas atmosphere in an aprotic solvent, for example acetone or methyl ethyl ketone, preferably under autogenous pressure, at temperatures of generally 50 to 130 ° C, preferably 60 to 100 ° C, particularly preferably 70 to 85 ° C with the diisocyanates. The reaction can optionally be accelerated by adding conventional catalysts. Preferred catalysts are amine-containing compounds such as 1,4-diaza (2,2,2) bicyclooctane (DABCO). Components A, B, C and optionally D are used in the amounts already mentioned above. The poly (ether-urethanes) obtained are then quaternized or protonated if a quaternized or protonated compound has not already been used as component B, for example compound III, IV or VIII.

Another object of the present application is thus a process for the preparation of a cationic poly (ether-urethane) according to the invention by reacting the at least one polyetherol and the at least one tertiary amine-containing or ammonium-containing diol with the at least one diisocyanate under an inert gas atmosphere in an aprotic solvent. If necessary, customary catalysts are added, and subsequent quaternization or protonation, if a quaternized or protonated tertiary ammonium-containing diol is not already used.

The protonation or quaternization generally takes place in a solvent at room temperature or at an elevated temperature, generally up to 50 ° C., if appropriate under pressure. Particularly suitable solvents are water and mixtures of water and water-miscible solvents, such as alcohols, ketones or cyclic ethers, for example ethanol, isopropanol, acetone, methyl ethyl ketone, dioxane or acetonitrile. The concentration of the solution depends solely on the solution behavior of the basic starting polyurethane mass and the salt-like end product.

Acids suitable for protonation are basically water and all acid-reacting compounds, i.e. H. Mineral acids or organic acids, especially carboxylic acids, phosphoric acids or sulfonic acids and their salts. Carboxylic acids are preferably used, in particular lactic acid. In protonation, acid is added according to the invention until the tertiary amino groups of the poly (ether-urethane) have been completely or partially neutralized in general up to a pH of 6 to 7.5.

The quaternization can be carried out, for example, with alkylating agents such as Cr to C ₄ alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate, with methyl chloride, dimethyl sulfate and diethyl sulfate being particularly preferred. Because of their cationic groups, the poly (ether-urethanes) according to the invention are generally readily soluble in alcohol and water or at least dispersible in water and alcohol without the aid of emulsifiers. Alcohols are understood here to mean, in particular, short-chain alkanols such as methanol, ethanol, isopropanol or n-propanol.

The poly (ether-urethanes) according to the invention are particularly suitable as foam regulating agents, that is to say as defoamers and / or foam suppressors.

The present application therefore furthermore relates to a liquid or solid composition comprising i) at least one cationic poly (ether-urethane) according to the invention, ii) at least one anionic surfactant, iii) optionally a liquid medium, and iv) optionally further auxiliaries and additives ,

While surfactants are deliberately added in detergents and cleaning agents to enable wetting and emulsification processes, in other formulations, for example paints, surfactants can be incorporated into the formulation via polymer dispersions. Polymer dispersions per se are also preferred formulations.

The preparation of the composition according to the invention is known to the person skilled in the art. It is generally done by mixing the individual components. The composition according to the invention i) particularly preferably comprises 0.01 to 17% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.2 to 2.5% by weight of the at least one cationic poly ( ether-urethane), ii) 0.01 to 83% by weight, preferably 0.1 to 60% by weight, particularly preferably 0.5 to 47.5% by weight of the at least one anionic surfactant, iii) 0 up to 99.98% by weight, preferably 30 to 99.7% by weight, particularly preferably 50 to 99.3% by weight of the liquid medium, the total sum of the components according to i), ii) and iii ) Is 100% by weight, iv) optionally further auxiliaries and additives. Cationic poly (ether-urethane)

The cationic poly (ether-urethane) according to the invention has been described in detail above. All of the cationic poly (ether-urethanes) described above are suitable in the compositions according to the invention. Preferred cationic poly (ether-urethanes) have also already been mentioned above.

Anionic surfactant

All anionic surfactants known to the person skilled in the art are suitable as anionic surfactants. The anionic surfactants preferably have a pK _a value of <7. The anionic surfactants are particularly preferably selected from at least one compound from the group consisting of linear alkylbenzenesulfonates, branched alkylbenzenesulfonates, alkylsulfonates, the alkyl groups of which can be linear or branched and preferably have 8 to 22, particularly preferably 12 to 15, carbon atoms , Ether sulfates, the alkyl groups of which can be linear or branched and preferably have 10 to 16 carbon atoms, xylylsulfonates, alcohol sulfates, phosphonates, alkyl phosphates, naphthyl sulfonates, secondary alkyl sulfates, α-olefin sulfonates, sulfosuccinates, isethionates, carboxylates and diphenylated sulfonates, alkylated sulfonates, and alkylated sulfonates Soap. Most of these anionic surfactants are usually offered in the form of their ammonium and sodium salts, although anionic surfactants with other cations can also be used.

a) Alkylbenzenesulfonates

The alkylbenzenesulfonates suitable as anionic surfactants in the compositions according to the invention can be variable in their molecular weight, the alkyl chain length and the position of the alkyl chain on the phenyl group. Suitable alkylbenzenesulfonates are listed, for example, in WO 01/76729 and the citations mentioned therein.

Linear alkyl benzene sulfonates ("LAS") are commonly used in commercial cleaning products due to their effectiveness as cleaning agents, their easy biodegradability and their relatively low cost. The linear alkylbenzenesulfonates can be prepared by sulfonating linear alkylbenzene intermediates. Linear alkyl benzenes are prepared by methods known in the art, generally using either aluminum trichloride catalysts or hydrogen fluoride catalysts.

The linear alkylbenzenesulfonates preferably used in the compositions according to the present invention preferably have linear alkyl chains with 8 to 22 carbon atoms, particularly preferably 8 to 16 carbon atoms.

Particularly suitable linear alkylbenzenesulfonates are listed in WO 01/76729. Weakly branched alkylbenzenesulfonates, as described in WO 00/39058 and WO 99/05242, are also suitable.

b) Other suitable anionic surfactants

Further anionic surfactants suitable for use in the compositions according to the invention are also listed in WO 01/76729.

Additionally suitable alkylated diphenyl oxide, which are available under the name Doxfax ^® from Dow commercially. Also suitable are anionic surfactants which are usually used in emulsion polymerization. Suitable anionic surfactants for emulsion polymerization are known to the person skilled in the art.

Liquid medium

Suitable liquid media are, for example, media which are suitable for dissolving anionic surfactants. Examples of suitable liquid media are water, cyclic carbonates, oils, such as paraffin oils, for example diesel oil, cosmetic oils, for example essential oils, pine oil, methyl esters, limonene, aliphatic and aromatic hydrocarbons or mixtures of the liquid media mentioned. Particularly suitable are water, alkyl alcohols with 1 to 6 carbon atoms, especially straight-chain alkyl alcohol, for example methanol, ethanol, n-propanol, n-hexanol, branched alkyl alcohols containing 3 to 6 carbon atoms, for example isopropanol and sec-butanol, glycols, for Example propylene glycol, diglycols, for example propylene diglycol, and triglycols, for example triethylene glycol, glycol ether, for example play butylene glycol diethyl ether and dipropylene glycol methyl ether. Water is very particularly preferably used as the liquid medium. The reactive solvents used in paints, for example bisphenol A ethoxylates, can also be used.

Auxiliaries and additives

Non-ionic surfactants, for example, can be used as auxiliaries and additives. Suitable nonionic surfactants are, for example, nonylphenol ethoxylates, alcohol ethoxylates, ethylene oxide / propylene oxide block copolymers, alcohol-ethylene oxide / propylene oxide adducts and mixtures thereof. Special suitable nonionic surfactants are mentioned for example in WO 01/76729.

Other auxiliaries and additives are, for example, dyes, fragrances, fillers, particles as dispersions, oils as emulsions, active ingredients in molecular solution, solubilized, as dispersions, emulsions or suspoemulsions, dispersing aids, for example water-soluble polymers, and thickeners , The compounds suitable for the particular composition are known to the person skilled in the art. Furthermore, for example, optical brighteners, dye transfer inhibitors, enzymes, builders, chelation reagents and other additives known to the person skilled in the art and suitable for use in surfactant compositions are suitable.

Because of the cationic poly (ether-urethane) used according to the invention, the compositions according to the invention have a reduced foam formation or a reduction in the foam formed or are suitable for foam regulation.

The cationic poly (ether-urethane) according to the invention thus serves as a foam regulator.

Another object of the present invention is thus a method for foam regulation, in particular for suppressing and / or reducing foam in a system containing a liquid medium, preferably water, and at least one anionic surfactant and optionally further auxiliaries and additives by adding at least one cationic Poly (ether-urethane) built up from a) at least one polyetherol, as component A, b) at least one tertiary aminodiol, as component B, c) at least one diisocyanate, as component C, and d) optionally at least one stopper, as component D.

Preferred cationic poly (ether-urethanes), solvents and anionic surfactants and suitable auxiliaries and additives have already been mentioned above.

The cationic poly (ether-urethane) can be added to the composition before the appearance of foam. However, it is also possible to add the cationic poly (ether-urethane) only after foaming has already taken place.

Another object of the present invention is the use of the cationic poly (ether-urethane) as a foam regulating agent, in particular as a defoamer and / or foam suppressor in systems containing a liquid medium, preferably water, and at least one anionic surfactant and optionally other auxiliaries and additives.

As already mentioned above, the cationic poly (ether-urethane) can be used in such a way that it is already present in the compositions whose foam formation is to be controlled before the occurrence of foam. However, the cationic poly (ether-urethane) can also be added after the appearance of foam.

Preferred cationic poly (ether-urethanes), solvents, anionic surfactants and suitable auxiliaries and additives have already been mentioned above.

The cationic poly (ether-urethanes) according to the invention can be used in all compositions containing at least one anionic surfactant in which foam regulation, in particular defoaming and / or foam suppression, is desired. Such compositions are preferably detergent compositions for machine cleaning or hand cleaning of laundry, dishes, bottles and / or automobiles, dispersions, in particular adhesive dispersions, lacquers or paint dispersions, emulsions, cosmetics, fermentation foams and agricultural formulations. Suitable components of these compositions in addition to the cationic poly (ether-urethane) according to the invention are known to the person skilled in the art.

The present invention therefore furthermore relates to the use of a cationic poly (ether-urethane) according to the invention for controlling the formation of foam in systems comprising a liquid medium, preferably an aqueous medium, and at least one anionic surfactant and optionally further auxiliaries and additives. The control of foam formation is preferably carried out by defoaming or suppressing foam formation.

Preferred systems, in particular aqueous systems, have already been mentioned above.

The following examples further illustrate the invention.

Examples

Preparation of the cationic poly (etherurethane) according to the invention

example 1

Starting materials: 58.5 g (0.065 mol) Pluriol P900 4.2 g (0.035 mol) N-methyldiethanolamine (N-MDEA) 20 g methyl ethyl ketone (MEK) 0.2 g 1, 4-diaza (2.2.2) bicyclooctane (DABCO)

16.8 g (0.1) hexamethylene diisocyanate (HDI) 3.9 g lactic acid (90%) 80 g water

58.5 g Pluriol P900, 4.2 g N-MDEA and 0.2 g DABCO are placed in 20 g MEK. The template is heated to a temperature of approx. 65 ° C with stirring. Hexamethylene diisocyanate is added in 15 minutes. The mixture becomes slightly exothermic. The reaction mixture is then stirred at 80 ° C. for a further 3 to 5 hours until the NCO content is constant. The reaction melt is then neutralized with lactic acid / water and diluted. Methyl- ethyl ketone is removed under vacuum. A slightly cloudy, approximately 50% dispersion is obtained.

Examples 2 to 4 were carried out in accordance with a corresponding specification, the various examples differing in the features given in Table 1 below:

Table 1 shows the composition of cationic poly (ether-urethanes) according to the invention and the protonating agent used.

Λ l - Table 1:

Pluriol P900: polypropylene glycol Mw weight average molecular weight «900 g / mol

N-MDEA: n-methyldiethanolamine NN-DMEA: dimethylethanolamine HDI hexamethylene diisocyanate K value K value according to H. Fikentscher (determined in 1% by weight solutions in N-methyl-pyrrolidone at 25 ° C and pH 7) (1 % strength)

Example 5

The cationic poly (ether-urethanes) according to the invention according to Examples 1 to 4 were tested in a circulation foam test (CNOMO foam test; provisional EU standard: prEN 14371).

Test conditions: 25 ° C 200 l / h run (button position: 7.0) pump for 10 minutes; Let stand for 5 minutes; 500 ml liquor (with bidistilled water) 0.1 g / l Lutensol A-LBN 50 (alkyl-benzenesulfonate Na salt) 0.005 g / l polyurethane

The test results are shown in Table 2 below, no defoamer or foam suppressor being added in comparative test 1. Table 2:

It can be seen that the cationic poly (ether-urethanes) (PU) according to the invention either suppress the foam volume (Example 2) or reduce the foam stability (Examples 1, 2 and 4).

Example 6 Defoaming of a heavy-duty detergent

A commercially available detergent formulation (anionic surfactant, nonionic surfactant, zeolite, fillers) was examined in the whipped foam test (EN 12728; measurement conditions: 2% by weight surfactant, 25 ° C., 200 ml liquor). a) without defoamer b) 0.5% by weight of the cationic poly (ether-urethane) from Example 3 c) sales product (commercial detergent)

The following foam volumes were measured: a) 175 cm ³ b) 90 cm ³ c) 150 cm ³ .

Claims

claims

1. Cationic poly (ether-urethane) composed of a) at least one polyetherol, as component A; b) at least one tertiary amine-containing or ammonium-containing diol, as component B; c) at least one diisocyanate as component C; d) optionally at least one stopper, as component D; wherein the cationic poly (ether-urethane) has an amine number from 5 to 40.

2. Cationic poly (ether-urethane) according to claim 1, characterized in that the cationic poly (ether-urethane) has a Fikentscher K value of 15 to 40.

3. Cationic poly (ether-urethane) according to claim 1 or 2 containing a) 50 to 90 wt .-%, preferably 55 to 85 wt .-%, particularly preferably 60 to 80, of component A; b) 1 to 10% by weight, preferably 2 to 7% by weight, particularly preferably 2.5 to 5% by weight of component B; c) 9 to 25% by weight, preferably 14 to 23% by weight, particularly preferably 17 to 21% by weight of component C; d) 0 to 15% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.3 to 5, of component D, the total sum of components A to D giving 100% by weight.

4. Cationic poly (ether-urethane) according to one of claims 1 to 3, characterized in that component A is selected from the group consisting of poly (C ₃ - to C ₅ -) glycols, polytetrahydrofuran, mixtures of the aforementioned compounds, Mixtures of at least one of the abovementioned compounds with polyethylene glycol, mixed polyalkylene glycols which are obtained by polymerizing various alkylene oxides and copolymers of at least one alkylene oxide with THF.

5. Cationic poly (ether-urethane) according to one of claims 1 to 4, characterized in that component B is selected from the group consisting of at least one compound of the formulas I, II, III and IV

HO-R- (III)

wherein R ¹ and R ^{2 are} alkylene, preferably C ₂ to C ₈ alkylene such as 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 2,2-dimethyl-1, 3-propylene, 1 , 2-propylene, 1, 2-butylene, 2,3-butylene, pentamethylene, hexamethylene, heptamethylene and octamethylene, R ³ , R ⁶ , R ⁷ and R ^{8 are} alkyl, aryl, alkylaryl or arylalkyl, preferably Cr to d- Alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, phenyl or C - to Cι ₀ - phenylalkyl such as benzyl, 2-phenylethyl, o -, m-, p-Methylbenzene, 3-phenylpropyl and 4-phenylbutyl.

6. Cationic poly (ether-urethane) according to any one of claims 1 to 5, characterized in that component C is selected from the group consisting of C ₂ - to Cβ-alkylene diisocyanates such as 1, 2-ethylene diisocyanate, 1, 4-butylene -diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate; C ₅ - to Cio-cycloalkylene diisocyanates such as 1,3-pentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate; 0-, m-, p-phenylene diisocyanate and (Cr to C ₄ alkyl) phenylene diisocyanates such as tolylene diisocyanate.

7. Cationic poly (ether-urethane) according to one of claims 1 to 6, characterized in that component D is selected from the group consisting of monofunctional amines, monofunctional alcohols, water and thiols.

8. Liquid or solid composition comprising i) at least one cationic poly (ether-urethane) according to one of claims 1 to 7, ii) at least one anionic surfactant, iii) optionally a liquid medium, and iv) optionally further auxiliaries and additives.

9. The composition according to claim 8, characterized in that the composition of 0.01 to 17 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.2 to 2.5, of the cationic poly (ether) urethane), 0.01 to 83% by weight, preferably 0.1 to 60% by weight, particularly preferably 0.5 to 47.5%, of the anionic surfactant, 0 to 99.98% by weight, preferably 30 to Contains 99.7% by weight, particularly preferably 50 to 99.3, of the liquid medium and optionally further auxiliaries and additives, the total sum of the components according to i), ii) and iii) giving 100% by weight ,

10. The composition according to claim 8 or 9, characterized in that the at least one anionic surfactant is selected from at least one compound from the group consisting of linear alkylbenzenesulfonates, branched alkylbenzenesulfonates, alkylsulfonates, ether sulfates, xylylsulfonates, alcohol sulfates, phosphate esters , Naphthyl sulfonates, secondary alkyl sulfates, α-olefin sulfonates, sulfosuccinates, isethionates, carboxylates alkylated diphenyloxide disulfonates and soaps.

11. The composition according to any one of claims 8 to 10, characterized in that the liquid medium is water.

12. Process for foam regulation, in particular for defoaming or for suppressing foam in a system containing a liquid medium, preferably water, at least one anionic surfactant and optionally further auxiliaries and additives by adding at least - üü - a cationic poly (ether-urethane) according to any one of claims i to 7.

13. Use of a cationic poly (ether-urethane) according to any one of claims 1 to 7 as a foam regulating agent, in particular as a defoamer and / or foam suppressor in a system containing a liquid medium, preferably water, and at least one anionic surfactant and optionally further auxiliaries and additives.

14. Use according to claim 12, characterized in that the system is a detergent composition for machine cleaning or hand cleaning of laundry, dishes, bottles, and / or cars, or a dispersion such as adhesive dispersion, paint and dye dispersion, emulsion, cosmetics, fermentation foams or agroformulation tion.

15. Use of a cationic poly (ether-urethane) according to any one of claims 1 to 7 for controlling foam formation in systems containing a liquid medium, preferably water, and at least one anionic surfactant and optionally other auxiliaries and additives.

16. A method for producing a cationic poly (ether-urethane) according to any one of claims 1 to 7, by reacting the at least one polyetherol and the at least one tertiary amine-containing or ammonium-containing diol with the at least one diisocyanate under an inert gas atmosphere in one aprotic solvent, with customary catalysts optionally being added, and subsequent quaternization or protonation if a quaternized or protonated tertiary ammonium-containing diol is not already used.