US20070245498A1

US20070245498A1 - Diethyl Methyl Ammonium Nitriles and Detergents and Cleaning Agents Containing Said Ammonium Nitriles

Info

Publication number: US20070245498A1
Application number: US11/661,489
Authority: US
Inventors: Gerd Reinhardt; Georg Borchers; Lars Cuypers; Ekaterina Jonas; Alexander Lerch; Michael Seebach
Original assignee: Individual
Current assignee: Individual
Priority date: 2004-08-28
Filing date: 2005-08-24
Publication date: 2007-10-25
Also published as: WO2006024434A1; JP2008511701A; EP1784385A1; DE102004041760A1

Abstract

Diethylmethylammonionitriles of the formula (1)

in which A is an anion are claimed. These compounds are suitable as a bleach activator in washing and cleaning compositions.

Description

This invention relates to odor-neutral short-chain ammonionitriles, to their granules and to their use for enhancing the bleaching action of peroxygen compounds in the bleaching of colored stains both on textiles and on hard surfaces, and to washing and cleaning compositions which comprise these nitriles as bleach activators.
Inorganic peroxygen compounds, especially hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have been used for some time as oxidizing agents for disinfection and bleaching purposes. The oxidizing action of these substances depends greatly upon the temperature in dilute solutions; for example, sufficiently rapid bleaching of soiled textiles is achieved with hydrogen peroxide or perborate in alkaline bleaching liquors only at temperatures above about 80° C.
It is known that the oxidative action of peroxidic bleaches, such as perborates, percarbonates, persilicates and perphosphates, at low temperatures can be improved by adding precursors of bleaching peroxy acids, known as bleach activators. According to the prior art, many substances are known to be bleach activators. They are usually reactive organic compounds having an O-acyl or N-acyl group, which form the corresponding peroxy acids in alkaline solution together with a source for hydrogen peroxide.
Representative examples of bleach activators are, for instance, N,N,N′,N′-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglycoluril (TAGU), 1-phenyl-3-acetylhydantoin (PAH), sodium nonanoyloxybenzenesulfonate (NOBS) and sodium isononanoyloxy-benzenesulfonate (ISONOBS). An interesting group is that of cationic compounds which contain a quaternary ammonium group, since they are highly effective bleach activators.
As a result of addition of these activators to an aqueous peroxide solution, perhydrolysis takes place with release of an organic peracid. This enhances the bleaching action of the solutions to such an extent that, even at temperatures between 40 and 60° C., they have essentially the same effects as a peroxide solution alone at 95° C.
A major disadvantage of the bleaching activators mentioned is that they usually leave behind bulky leaving groups (for example phenolsulfonates) on completion of perhydrolysis, which are of no significance whatsoever for the bleaching process.
From an ecological point of view, bleaching activators in which a highly reactive peracid but no leaving group is released in the perhydrolysis step are therefore of interest. This is achieved, for example, by a cyano group. This probably forms a peroxyimide acid in the perhydrolysis, which then acts as the bleaching agent.
Examples thereof are ammonionitriles, characterized by the structural element
Compounds of this type and their use as activators in bleaches are described in EP-A-303 520, EP-A-458 396 and EP-A-464 880. Ammonionitriles where two of the R¹, R²or R³groups are a long-chain alkyl group are claimed in WO 03/078561.
However, low molecular weight ammonionitriles having a total of not more than 12 carbon atoms are of particular interest, since they have excellent water solubility, are highly reactive and are simultaneously particularly weight-effective. The latter plays a particular role in volume-effective washing compositions with low dosage. There has therefore been no lack of attempts in the past to prepare such compounds. Numerous patent applications therefore describe the use of trimethylammonioacetonitriles of the formula

where X⁻ is an anion, for example chloride, sulfate, hydrogensulfate, methylsulfonate, ethanesulfonate, toluenesulfonate, benzenesulfonate or cumenesulfonate. Examples of the synthesis, granulation and use of these trimethylammonioacetonitriles can be found in WO 02/012175, WO 02/012427, DE 100 38 844 or EP 13 12 665.
A serious disadvantage of all trimethylammonioacetonitriles is, however, that they release, under alkaline conditions, whether they be in the wash liquor or in the course of prolonged storage in an alkaline washing composition, traces of trimethylamine and hence a fishy odor which makes their use in the household sector impossible. There has therefore been no lack of attempts to prepare odor-free trimethylammonioacetonitriles, for example by exchange of the anion or by deodorization, as described in DE 102 24 509.
Surprisingly, even the higher homolog (dimethylethylammonioacetonitrile tosylate) releases traces of trimethylamine under alkaline conditions. As a result of alkaline treatment, traces of trimethylamine can be detected even from N-methylmorpholinioacetonitrile methosulfate. The mechanism of the formation is unclear, but one of the methyl groups bonded to a nitrogen atom is probably transferred to ammonia which is released as a result of hydrolysis of the nitrile. Repeated methyl group transfer then forms traces of trimethylamine.
It has now been found that, surprisingly, N-methylammonionitriles of the above-described type which have two ethyl substituents are effective bleach activators which do not form trimethylamine under alkaline conditions even though a methyl group resides on the nitrogen.
The present invention thus provides compounds of the general formula

where X⁻ is an anion, for example chloride, bromide, sulfate, hydrogen-sulfate, methosulfonate, ethanesulfonate, toluenesulfonate, benzene-sulfonate or cumenesulfonate. Particular preference is given to the chloride, hydrogensulfate, sulfate, methosulfate and toluenesulfonate anions.
The synthesis routes for the diethylmethylammonioacetonitriles of this invention will be illustrated with reference to a few general examples:
1. Diethylamine is initially charged together with a base, preferably alkali metal carbonate or alkali metal hydroxide, in a solvent, preferably in absolute ethanol or in a toluene/water mixture. At temperatures between 0 and 50° C., preferably at from 10 to 30° C., chloroacetonitrile is added dropwise. After from 1 to 50 hours of reaction time, the organic phase is removed and the aqueous phase is extracted with an organic solvent. The solvent is removed from the combined organic phases. The resulting crude product can be purified further by fractional distillation. The diethylaminoacetonitrile formed is taken up in water or an organic solvent and reacted with an alkylating agent such as methyl chloride, dimethyl sulfate or methyl p-toluenesulfonate at temperatures between 20 and 100° C. to give the corresponding N-cyanomethylammonium salt. The salt can be obtained by conventional methods of workup, such as extraction, crystallization, suction filtration, washing of the crystal slurry on the suction filter and drying. It is possible to proceed analogously from ethylmethylamine, in which case the quaternization is performed with an ethyl derivative.
2. Diethylmethylamine and chloroacetonitrile are reacted in a suitable solvent, for example in acetone, at temperatures between 10 and 70° C. for from 1 to 12 hours. The precipitate formed, the N-cyano-methylammonium chloride, is filtered off, washed with an organic solvent and dried.
3. Diethylamine, sodium cyanide and an aldehyde or a ketone, preferably formaldehyde in the form of a 36% formalin solution, are combined in a solvent, preferably an ethanol/water mixture or water.
After a reaction time of from 1 to 12 hours at temperatures between 10 and 80° C., preferably at from 10 to 30° C., aqueous hydrochloric acid is added to the mixture. The aqueous phase is extracted with a suitable organic solvent, for example methylene chloride or diethyl ether. After drying over magnesium sulfate, the solvent is removed from the combined organic phases. The resulting crude product can be purified further by fractional distillation. The dialkylamino-acetonitrile formed is taken up in an organic solvent and reacted with an alkylating agent such as methyl chloride, dimethyl sulfate or alkyl arylsulfonate at temperatures between 20 and 100° C. to give the corresponding N-cyanomethylammonium salt. The salt can be obtained by conventional methods of workup, such as extraction, crystallization, suction filtration, washing of the crystal slurry on the suction filter and drying. It is possible to proceed analogously from ethylmethylamine, in which case the quaternization is performed with an ethyl derivative.
The invention also provides for the use of these ammonionitriles as bleach activators in bleaching washing and cleaning compositions. In a particular embodiment, the inventive diethylmethylammonioacetonitrile is used in the form of a granule in washing and cleaning compositions. Such granules may contain from 5 to 95% by weight, but preferably from 20 to 90% by weight, of the inventive diethylmethylammonioacetonitrile. As further constituents, such a granule may comprise a further bleach activator. Preference is given here to decanoyloxybenzoic acid, sodium nonanoyloxybenzenesulfonate, tetraacetylethylenediamine or 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine. In addition, granulating aids and/or coating materials may be employed for the formation of the granule.
The term “bleaches” here is understood to mean both the bleaching of soil on the textile surface and the bleaching of soil in the wash liquor which has been detached from the textile surface. For the bleaching of stains on hard surfaces, the same applies mutatis mutandis. Further potential applications are within the personal care sector, for example in the bleaching of hair and for the improvement in the effectiveness of denture-cleaning compositions. In addition, the inventive complexes find use in commercial laundries, in wood- and paper-bleaching, the bleaching of cotton and in disinfectants.
The invention further relates to a process for cleaning textiles and also hard surfaces, especially of dishwave, using the cationic nitriles mentioned in aqueous solution optionally comprising further washing composition or cleaning composition constituents, in particular peroxygen-based oxidizing agents, and also to washing or cleaning compositions for hard surfaces, especially cleaning compositions for dishes, preference being given to those for use in machine processes, which comprise such cationic nitriles.
The inventive use consists substantially in creating conditions in the presence of hard surfaces contaminated with colored stains or of a correspondingly soiled textile, under which a peroxidic oxidizing agent and the cationic nitrile can react with one another, with the aim of obtaining more strongly oxidizing conversion products. Such conditions are present especially when the reaction partners meet one another in aqueous solution. This can be done by separately adding the peroxygen compound and the cationic nitrile to a solution optionally containing washing or cleaning composition. However, the process according to the invention becomes particularly advantageous with the use of a washing composition or cleaning composition for hard surfaces, which comprises the cationic nitrites and optionally a peroxygen-containing oxidizing agent. The peroxygen compound may also be added to the solution separately in substance or as a preferably aqueous solution or suspension when a peroxygen-free washing or cleaning composition is used.
The inventive washing and cleaning compositions, which may be present in the form of granules, pulverulent or tableted solids, in the form of other shaped bodies, homogeneous solutions or suspensions, may, apart from the bleach-boosting active ingredient mentioned and a peroxygen compound, in principle comprise all known ingredients which are customary in such compositions. The inventive compositions may in particular comprise builder substances, surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestrants, thickeners, preservatives, pearlescents, emulsifiers and enzymes, and also special additives having color care or fiber care action. Further assistants such as electrolytes, pH regulators, silver corrosion inhibitors, foam regulators and colorants and fragrances are possible.
Suitable peroxygen compounds are hydrogen peroxide and compounds which release hydrogen peroxide under the washing and cleaning conditions, such as alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts and inorganic per salts, such as alkali metal perborates, percarbonates, perphosphates, persilicates, persulfates and peroxynitrites. Mixtures of two or more of these compounds are likewise suitable. Particular preference is given to sodium perborate tetrahydrate and in particular sodium perborate monohydrate and sodium percarbonate. Owing to its good storage stability and its good solubility in water, sodium perborate monohydrate is preferred. Sodium percarbonate may be preferred for ecological reasons.
Alkali metal hydroperoxides are a further suitable group of peroxide compounds. Examples of these substances are cumene hydroperoxide and t-butyl hydroperoxide.
Aliphatic or aromatic mono- or dipercarboxylic acids and the corresponding salts are also suitable as peroxy compounds. Examples thereof are peroxynaphthoic acid, peroxylauric acid, peroxystearic acid, N,N-phthaloylaminoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-dioic acid and 4,4′-sulfonylbisperoxybenzoic acid.
In such washing and cleaning compositions, the inventive cationic nitrilic bleach activator may be present at a proportion by weight of from about 0.1 to 20%, preferably from 0.5 to 10%, in particular from 0.5 to 5.0%, together with a peroxy compound. The proportion by weight of this peroxy compound is usually from 2 to 40%, preferably from 4 to 30%, in particular from 10 to 25%.
The washing and cleaning compositions may comprise, as well as the inventive cationic nitrilic bleach activators, also other suitable bleach activators in the customary amounts (from approx. 1 to 10% by weight). Suitable bleach activators are organic compounds having an O-acyl or N-acyl group, especially from the group of the activated carboxylic esters, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyl-oxybenzenesulfonate, sodium 4-benzoyloxybenzenesulfonate, sodium trimethylhexanoyloxybenzenesulfonate, carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric, alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, lactones, acylals, carboxamides, acyllactams, acylated ureas and oxamides, N-acylated hydantoins, for example 1-phenyl-3-acetylhydantoin, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazides, sulfurylamides or polyacylated alkylenediamines, for example N,N,N′,N′-tetraacetylethylenediamine, acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxyhexahydro-1,3,5-triazine, acylated glycolurils, especially tetraacetylglycoluril, N-acylimides, especially N-nonanoylsuccinimide, and acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acylated, optionally N-alkylated glucamine and gluconolactone and/or N-acylated lactams, for example N-benzoylcaprolactam, but also quaternary nitrile compounds, for example quaternary trialkylammonionitrile salts, as described in EP-A-303 520, EP-A458 396 and EP-A464 880, especially the cyanomethyltrimethylammonium salt, but also heterocyclically substituted quaternary nitrile compounds, as described in EP-A-790 244.
In addition to the conventional bleach activators listed above or in their stead, it is also possible to use sulfonimines, open-chain or cyclic quaternary iminium compounds such as dihydroisoquinolinium betaines and/or further bleach-boosting transition metal salts or mono- or polycyclic transition metal complexes with acyclic or macrocyclic ligands.
The washing and cleaning compositions may comprise one or more surfactants, and useful surfactants are in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants. Such surfactants are present in the inventive washing compositions in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas cleaning compositions for hard surfaces normally contain smaller proportions, i.e. amounts of up to 20% by weight, in particular of up to 10% by weight and preferably in the range from 0.5 to 5% by weight. Cleaning compositions for use in machine dishwashing processes are normally low-foaming compounds.
Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. Useful surfactants of the sulfonate type are preferably C₉-C₁₃-alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene- and hydroxyalkanesulfonates, and also disulfonates, as are obtained, for example, from monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C₁₂-C₁₈-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis and neutralization respectively. Also suitable are the esters of alpha-sulfo fatty acids (ester sulfonates) for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fat acids, which are prepared by sulfonating the methyl esters of fatty acids of vegetable and/or animal origin having from 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to give water-soluble monosalts.
Further suitable anionic surfactants are sulfated fatty acid glycerol esters which are mono-, di- and triesters, and mixtures thereof. Preferred alk(en)yl sulfates are the alkali metal and in particular the sodium salts of the sulfuric monoesters of the C₁₂-C₁₈-fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of the C₈-C₂₀-oxo alcohols and those monoesters of secondary alcohols of this chain length. Also preferred are alk(en)yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis. 2,3-Alkyl sulfates are also suitable anionic surfactants. Also suitable are the sulfuric monoesters of the straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C₉-C₁₁-alcohols with on average 3.5 mol of ethylene oxide (EO) or C₁₂-C₁₈fatty alcohols having from 1 to 4 EO.
The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid which are also referred to as sulfosuccinates or as sulfosuccinic esters, and the mono- and/or diesters of sulfosuccinic acid with alcohols, preferably with fatty alcohols and in particular with ethoxylated fatty alcohols. Preferred sulfosuccinates contain C₈-C₁₈fatty alcohol radicals or mixtures of these. Useful further anionic surfactants include fatty acid derivatives of amino acids, for example of N-methyltaurine (taurides) and/or of N-methylglycine (sarcosinates). Useful further anionic surfactants include in particular soaps, for example in amounts of from 0.2 to 5% by weight. Especially suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and also in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fat acids.
The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts, and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Anionic surfactants are present in inventive washing compositions preferably in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.
The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably from 8 to 18 carbon atoms and on average from 1 to 12 mol of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or preferably 2-methyl-branched, or may contain linear and methyl-branched radicals in a mixture, as are typically present in oxoalcohol radicals. However, especially preferred are alcohol ethoxylates having linear radicals from alcohols of native origin having from 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, C₁₂-C₁₄-alcohols having 3 EO or 4 EO, C₉-C₁₁-alcohols having 7 EO, C₁₃-C₁₅-alcohols having 3 EO, 5 EO, 7 EO or 8 EO, C₁₂-C₁₈-alcohols having 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C₁₂-C₁₄-alcohol having 3 EO and C₁₂-C₁₈-alcohol having 7 EO. The degrees of ethoxylation specified constitute statistical averages which may be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols having more than 12 EO may also be used. Examples thereof are (tallow) fatty alcohols having 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
The nonionic surfactants also include alkylglycosides of the general formula RO(G)_xin which R is a primary, straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having from 8 to 22, preferably from 12 to 18, carbon atoms, and G is a glycoside unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x which specifies the distribution of monoglycosides and oligoglycosides is an arbitrary number, which may also assume fractional values as a quantity to be determined analytically, between 1 and 10; x is preferably from 1.2 to 1.4. Likewise suitable are polyhydroxy fatty acid amides of the formula (I) in which the R¹CO radical is an aliphatic acyl radical having from 6 to 22 carbon atoms, R²is hydrogen, an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having from 3 to 10 carbon atoms and from 3 to 10 hydroxyl groups.
The polyhydroxy fatty acid amides preferably derive from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of the polyhydroxy fatty acid amides also includes compounds of the formula (II) R³is a linear or branched alkyl or alkenyl radical having from 7 to 12 carbon atoms, R⁴is a linear, branched or cyclic alkylene radical or an arylene radical having from 2 to 8 carbon atoms and R⁵is a linear, branched or cyclic alkyl radical or an aryl radical, or an oxyalkyl radical having from 1 to 8 carbon atoms, preference being given to C₁-C₄-alkyl or phenyl radicals, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical. [Z] is obtained here too preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds may then be converted to the desired polyhydroxy fatty acid amides by reacting with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
A further class of nonionic surfactants used with preference, which may be used either as the sole nonionic surfactant or in combination with other nonionic surfactants, especially together with alkoxylated fatty alcohols and/or alkylglycosides, is that of alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide and of the fatty acid alkanolamides may also be suitable.
Useful further surfactants are what are known as gemini surfactants. This generally refers to those compounds which have two hydrophilic groups per molecule. These groups are generally separated from one another by a “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups have a sufficient separation and they can act independently of one another. Such surfactants generally feature an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of water. However, it is also possible to use gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Further surfactant types may have dendrimeric structures.
Suitable organic and inorganic builders are neutral or especially alkaline salts which can precipitate or complex calcium ions. Suitable builder substances which are in particular ecologically uncontroversial are crystalline sheet-type silicates of the general formula NaMSi_(x)O_(2x+1), where M is sodium or hydrogen, x is from 1.9 to 22, preferably from 1.9 to 4, and y is from 0 to 33, for example Na-SKS-5 (α-Na₂Si₂O₅), Na-SKS-7 (β-Na₂Si₂O₅, natrosilite), Na-SKS-9 (NaHSi₂O₅*H₂O), Na-SKS-10 (NaHSi₂O₃*3H₂O, kanemite), Na-SKS-11 (t-Na₂Si₂O₅) and Na-SKS-13 (NaHSi₂O₅), but in particular Na-SKS-6 (δ-Na₂Si₂O₅), and also finely crystalline synthetic water-containing zeolites, especially of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO/g.
Zeolites and sheet silicates may be present in an amount of up to 20% by weight in the composition.
Additionally suitable are non-neutralized or partly neutralized (co)polymeric polycarboxylic acids. These include the homopolymers of acrylic acid or of methacrylic acid or copolymers thereof with further ethylenically unsaturated monomers, for example acrolein, dimethylacrylic acid, ethylacrylic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, meth(allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, and monomers containing phosphorus groups, for example vinylphosphoric acid, allylphosphoric acid and acrylamidomethylpropanephosphoric acid and salts thereof, and also hydroxyethyl (meth)acrylate sulfate, allyl alcohol sulfate and allyl alcohol phosphates.
Preferred (co)polymers have a mean molar mass of from 1000 to 100 000 g/mol, preferably from 2000 to 75 000 g/mol and in particular from 2000 to 35 000 g/mol.
The degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.
The suitable polymers include in particular also homopolymers of acrylic acid and copolymers of (meth)acrylic acid with maleic acid or maleic anhydride.
Further suitable copolymers derive from terpolymers which can be obtained by polymerizing from 10 to 70% by weight of monoethylenically unsaturated dicarboxylic acids having from 4 to 8 carbon atoms, salts thereof, from 20 to 85% by weight of monoethylenically unsaturated monocarboxylic acids having from 3 to 10 carbon atoms or salts thereof, from 1 to 50% by weight of monounsaturated monomers which, after hydrolysis, release hydroxyl groups on the polymer chain, and from 0 to 10% by weight of further free-radically copolymerizable monomers.
Likewise suitable are graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides, and also animal or vegetable proteins.
Preference is given to copolymers of sugar and other polyhydroxyl compounds and a monomer mixture composed of from 45 to 96% by weight of monoethylenically unsaturated C₃- to C₁₀-monocarboxylic acids or mixtures of C₃- to C₁₀-monocarboxylic acids and/or salts thereof with monovalent cations, from 4 to 55% by weight of monomers containing monoethylenically unsaturated monosulfonic acid groups, monoethylenically unsaturated sulfuric esters, vinylphosphoric esters and/or the salts of these acids with monovalent cations, and from 0 to 30% by weight of water-soluble unsaturated compounds which have been modified with from 2 to 50 mol of alkylene oxide per mole of monoethylenically unsaturated compounds.
Further suitable polymers are polyaspartic acid and derivatives thereof in non-neutralized or only partly neutralized form.
Also particularly suitable are graft polymers of acrylic acid, methacrylic acid, maleic acid and further ethylenically unsaturated monomers onto salts of polyaspartic acid, as typically obtained in the above-described hydrolysis of the polysuccinimide. It is possible here to dispense with the otherwise necessary addition of acid for the preparation of the only partly neutralized form of the polyaspartic acid. The amount of polyaspartate is typically selected such that the degree of neutralization of all carboxyl groups incorporated in the polymer does not exceed 80%, preferably 60%.
Further usable builders are, for example, the carboxylic acids used preferably in the form of their sodium salts, such as citric acid, especially trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, mono-, dihydroxysuccinic acid, α-hydroxy-propionic acid, gluconic acid, mellitic acid, benzopolycarboxylic acids, and those as disclosed in U.S. Pat. Nos. 4,144,226 and 4,146,495.
Also suitable are phosphate-containing builders, for example alkali metal phosphates, which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts.
Examples thereof are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogenphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization in the range from 5 to 1000, in particular from 5 to 50, and mixtures of sodium and potassium salts.
These builder substances may be present from 5 to 80% by weight; preference is given to a proportion of from 10 to 60% by weight.
The desired viscosity of the liquid compositions can be established by adding water and/or organic solvents or by adding a combination of organic solvents and thickeners.
In principle, useful organic solvents are all mono- or polyhydric alcohols. Preference is given to using alcohols having from 1 to 4 carbon atoms, such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned. Further preferred alcohols are polyethylene glycols having a relative molecular mass below 2000. Preference is given in particular to use of polyethylene glycol having a relative molecular mass between 200 and 600 and in amounts up to 45% by weight, and of polyethylene glycol having a relative molecular mass between 400 and 600 in amounts of from 5 to 25% by weight. An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol, and polyethylene glycol in a ratio of from 0.5:1 to 1.2:1.
Further suitable solvents are, for example, triacetin (glyceryl triacetate) and methoxy-2-propanol.
The thickeners used are preferably hydrogenated castor oil, salts of long-chain fatty acids, which are used preferably in amounts of from 0 to 5% by weight and in particular in amounts of from 0.5 to 2% by weight, for example sodium stearate, potassium stearate, aluminum stearate, magnesium stearate and titanium stearate, or the sodium and/or potassium salts of behenic acid, and also polysaccharides, especially xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, and also relatively high molecular weight poly-ethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, and also electrolytes such as sodium chloride and ammonium chloride.
Suitable thickeners are water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular mass of above one million. Examples thereof are the polymers obtainable under the name Carbopol® 940 and 941. The cross-linked polyacrylates are used in amounts of not more than 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight.
The enzymes optionally present in the inventive compositions include proteases, amylases, pullulanases, cellulases, cutinases and/or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and/or Savinase®, amylases such as Termamy®, Amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and/or the cellulases and/or lipases disclosed by the international patent applications WO 96/34108 and WO 96/34092, such as Lipolase®, Lipomax®, Lumafast® and/or Lipozym®. The enzymes used may, as described, for example, in the international patent applications WO 92/111347 or WO 94/23005, be adsorbed on carriers and/or embedded in coating substances in order to protect them from premature inactivation. They are present in inventive washing and cleaning compositions preferably in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, particular preference being given to the use of enzymes stabilized against oxidative degradation.
Inventive machine dishwasher detergents preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and/or alkali metal hydrogencarbonates. The customarily used alkali carriers include carbonates, hydrogencarbonates and alkali metal silicates having a molar SiO₂/M₂O ratio (M=alkali metal atom) of from 1:1 to 2.5:1. Alkali metal silicates may be present in amounts of up to 40% by weight, in particular from 3 to 30% by weight, based on the overall composition. The alkali carrier system used with preference in the inventive cleaning compositions is a mixture of carbonate and hydrogencarbonate, preferably sodium carbonate and hydrogencarbonate which may be present in an amount of up to 50% by weight, preferably from 5 to 40% by weight.
The invention further provides a composition for the machine washing of dishes, containing from 15 to 65% by weight, in particular from 20 to 60% by weight, of water-soluble builder component, from 5 to 25% by weight, in particular from 8 to 17% by weight, of oxygen-based bleach, based in each case on the overall composition, and from 0.1 to 5% by weight of one or more of the above-defined cationic nitrilic activators. Such a composition is preferably slightly alkaline, i.e. its percent by weight solution has a pH of from 8 to 11.5, in particular from 9 to 11.
In a further embodiment of inventive compositions for the automatic washing of dishes, from 20 to 60% by weight of water-soluble organic builders, in particular alkali metal citrate, from 3 to 20% by weight of alkali metal carbonate and from 3 to 40% by weight of alkali metal disilicate are present.
In order to bring about silver corrosion protection, it is possible to use silver corrosion inhibitors in inventive cleaning compositions for dishes. Preferred silver corrosion protectants are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, salts and/or complexes of titanium, zirconium, hafnium, molybdenum, vanadium or cerium.
When the compositions foam too vigorously on use, it is possible also to add to them up to 6% by weight, preferably from about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group comprising silicones, paraffins, paraffin-alcohol combinations, hydrophobized silicas, fatty acid bisamides and mixtures thereof, and other known commercially available foam inhibitors. The foam inhibitors, especially silicone- and/or paraffin-containing foam inhibitors, are preferably bound to a granular carrier substance soluble or dispersible in water. Special preference is given to mixtures of paraffins and bistearylethylenediamide. Further optional ingredients in the inventive compositions are, for example, perfume oils.
The organic solvents which can be used in the inventive compositions, especially when they are present in liquid or pasty form, include alcohols having from 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having from 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and mixtures thereof and the ethers derivable from the compound classes mentioned. Such water-miscible solvents are present in the inventive cleaning compositions preferably to an extent of not more than 20% by weight, in particular from 1 to 15% by weight.
To set a desired pH which does not arise automatically by the mixing of the remaining components, the inventive compositions may comprise system- and environment-compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, especially sulfuric acid or alkali metal hydrogensulfates, or bases, especially ammonium or alkali metal hydroxides. Such pH regulators are present in the inventive compositions preferably to the extent of not more than 10% by weight, in particular from 0.5 to 6% by weight.
Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, pentanediol or sorbic acid.
Useful pearlescents include, for example, glycol distearic esters such as ethylene glycol distearate, but also fatty acid monoglycol esters. Useful salts and modifiers include, for example, sodium sulfate, sodium carbonate or sodium silicate (waterglass).
Typical individual examples of further additives include sodium borate, starch, sucrose, polydextrose, RAED, stilbene compounds, methyl-cellulose, toluenesulfonate, cumenesulfonate, soaps and silicones.
The inventive compositions are preferably in the form of pulverulent, granular or tableted preparations which can be produced in a known manner, for example by mixing, granulating, roll-compacting and/or by spray-drying the thermally stressable components, and mixing in the more sensitive components, which include in particular enzymes, bleaches and the bleach catalyst. Inventive compositions in the form of aqueous solutions or those comprising other customary solvents are particularly advantageously prepared by simply mixing the ingredients which can be introduced in substance or as a solution into an automatic mixer.
For the production of particulate compositions with increased bulk density, especially in the range from 650 g/l to 950 g/l, preference is given to a process which has an extrusion step and is disclosed by the European patent EP 0 486 592. A further preferred production method with the aid of a granulation process is described in the European patent EP 0 642 576. Inventive compositions in the form of nondusting, storage-stable free-flowing powders and/or granules having high bulk densities in the range from 800 to 1000 g/l can also be prepared by mixing, in a first process stage, the builder components with at least a portion of liquid mixture components while increasing the bulk density of this premixture, and subsequently, if desired after an intermediate drying, combining the further constituents of the composition, including the cationic nitrilic activator, with the thus obtained premixture.
To prepare the inventive compositions in tablet form, the procedure is preferably to mix all constituents with one another in a mixer and to compress the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses. In this way, tablets which are fracture-resistant and nevertheless sufficiently rapidly soluble under use conditions and have flexural strengths of normally above 150 N are obtained without any problem. A tablet prepared in this way preferably has a weight of from 1-5 9 to 40 g, in particular from 20 g to 30 g, at a diameter of from 3-5 mm to 40 mm.
In addition to the ingredients already mentioned, the washing and cleaning compositions may comprise each of the conventional additives in amounts which are typically found in such compositions.

EXAMPLES

Example 1

Synthesis of (cyanomethyl)diethylmethylammonium chloride

17.4 g (0.2 mol) of N,N-diethylmethylamine were initially charged in 100 ml of acetone. 15.1 g (0.2 mol) of chloroacetonitrile were added dropwise at RT to this solution within 10 min, in the course of which the temperature rose to 27° C. After about 5 min, the first precipitations became visible. The mixture was stirred at RT overnight, and the product was filtered off on a suction filter and washed with acetone. Subsequently, it was dried in a vacuum drying cabinet. This gave 20.4 g (0.125 mol; 63%) of (cyanomethyl)diethylmethylammonium chloride.
¹H NMR: δ=1.3 ppm (t, 6H, ethyl-CH₃); 3.2 (s, 3H, N—CH₃); 3.55 (q, 4H, ethyl-CH₂); 5.15 (s, 2H, N—CH₂—CN).

Example 2

Synthesis of (cyanomethyl)diethylmethylammonium methosulfate

22.4 g (0.2 mol) of diethylaminoacetonitrile were initially charged in 100 ml of ethyl acetate. 25.2 g (0.2 mol) of dimethyl sulfate were added dropwise at an internal temperature of 10-15° C. within 10 min with ice cooling. The reaction mixture was concentrated to dryness on a rotary evaporator (40° C.; 0.1 mbar). This gave 43.2 g (0.181 mol; 91%) of (cyanomethyl)diethylmethylammonium methosulfate.
¹H NMR: δ=1.3 ppm (t, 6H, ethyl-CH₃); 3.1 (s, 3H, N—CH₃); 3.4 (s, 3H, CH₃OSO₃); 3.5 (q, 4H, ethyl-CH₂); 4.85 (s, 2H, N—CH₂—CN).

Example 3

Synthesis of (cyanomethyl)diethylmethylammonium tosylate

56.1 g (0.5 mol) of diethylaminoacetonitrile were dissolved in 75 ml of toluene, and a solution of 93.1 g (0.5 mol) of methyl tosylate in 75 ml of toluene was added dropwise within 30 minutes. The reaction mixture was stirred under reflux for 4 hours. The reaction mixture was cooled to room temperature and the precipitated solid was filtered off. The filtercake was washed with 100 ml of toluene and the solid was dried at 60° C. under reduced pressure.
142.9 g (0.48 mol) of pure (cyanomethyl)diethylmethylammonium tosylate were obtained, corresponding to a yield of 95.8%.
m.p.: 115° C. ¹H NMR (D₂O): δ=7.65 (2H, d); δ=7.32 (2 H, d); δ=4.59 (2H, s); δ=3.51 (4H, q); 8 =3.14(3H, s); δ=2.35(3H, s); δ=1.34(6H, t)

Example 4

Production of a Granule

A laboratory plowshare mixer (Lödige M5R with bladed head) was initially charged with 875 g of (cyanomethyl)diethylmethylammonium tosylate powder which were heated to a temperature of T=60° C. at a mixer speed of n=100 min⁻¹. On attainment of the target temperature, the mixer speed was increased to n=250 min⁻¹, the bladed head was switched on and an amount of 125 g of a Genapol T-500 melt was metered into the mixer within 2 min. (Genapol T-500=fatty alcohol glycol ether−commercial product from Clariant GmbH.) The Genapol melt was heated to a temperature of T=80° C. before the metered addition. The product mixture was mixed for another approx. 30 sec after the introduction of the total amount of the melt, and then emptied from the mixer.
For the granulation, a laboratory annular pan-grinding press (Schluter PP 85) was used, which was equipped with a 1 mm die. Before the granulation, the essential working regions, die and pan grinder, were preheated to a temperature of T=60° C. The product mixture from the plowshare mixer was metered with a metering rate of approx. 80-100 g/min into the annular pan-grinding press which worked at a speed of n=300 min⁻¹. The distance between pan grinder and annular die was adjusted to approx. 0.4 mm; the distance of the stripper blade was adjusted to approx. 4 mm. The noodle-shaped granules formed had a temperature of approx. 65-70° C. and were cooled to room temperature before the further processing. Product was finally fractionated on a laboratory screen (Retsch AS 200 control) in order to remove fines <400 μm and coarse fractions >1600 μm from the target product. The finished noodle-shaped granule was present with a composition of 87.5% (cyanomethyl)diethylmethyl-ammonium tosylate and 12.5% Genapol T-500.

Example 5

Preparation of a cogranule of TAED and (cyanomethyl)diethylmethyl-ammonium tosylate

A laboratory mixer (Eirich R-02) was initially charged with 0.92 kg of TAED powder, 0.92 kg of (cyanomethyl)diethylmethylammonium tosylate powder and 0.16 kg of bentonite (for example Ikomont NA weiβ-commercial product from S&B Industrial Minerals GmbH). The products were mixed intensively at a mixing vessel speed of n=32 min⁻¹(level I) and a fluidizer speed of n=750 min⁻¹for 2 min.
The powder mixture thus produced was subsequently compressed in a roll compacter (Hosokawa-Bepex Pharmapaktor L 200/30 P). The speed of the rollers was varied in the range of approx. 4-8 min⁻¹and the speed of the stuffing screw within the range of approx. 18-25 min⁻¹, in order to ensure sufficient compacting of the powder. The compressed pieces were subsequently comminuted gently on a screening mill (Alexanderwerk SKM/NR), working with a screen insert having a mesh size of 1600 μm and a speed of 33 min⁻¹. The comminuted product was finally fractionated on a laboratory screen (Retsch AS 200 control), in order to remove fines <400 μm from the target product. The finished compactate was present with a composition of 46% TAED, 46% (cyanomethyl)-diethylmethylammonium tosylate and 8% bentonite.

Example 6

Odor Test

In each case 100 g of washing powder (Ariel, from Procter & Gamble) were introduced into 250 ml glass bottles and 5 g of a cyanomethylammonium salt were added in each case. Subsequently, the bottles were stored at 40° C. for 4 weeks. After this time, the odor of the washing powder was smelt by a test panel.



Cyanomethylammonium salt	Odor assessment

Cyanomethyltrimethylammonium chloride	very fishy
Cyanomethyldimethylethylammonium tosylate	slightly fishy
Cyanomethyldiethylmethylammonium tosylate	neutral
(according to Example 3)

The inventive cyanomethylammonium salt has no fishy odor and is therefore suitable for use in commercial products.

Example 7

Analytical Detection of Trimethylamine formed from Cyanomethylammonium Salts under Alkaline Conditions

A 100 mg sample of the cyanomethylammonium salts was dissolved in 100 μl of water and 2 ml of a 20% sodium carbonate solution and then stored at 70° C. for 16 h. Subsequently, the content of the trimethylamine (TMA) formed was determined by means of gas chromatography.



Cyanomethylammonium salt	TMA after reaction

Cyanomethyltrimethylammonium tosylate	26 ppm
Cyanomethyldimethylethylammonium tosylate	20 ppm
Methylmorpholinoacetonitrile methosulfate	3 ppm
Cyanomethyldiethylmethylammonium tosylate	0 ppm

Example 8

Bleaching Performance of Cyanomethyltrialkylammonium Salts
The bleaching performance of the cyanomethyltrialkylammonium salts was examined in a Linitest unit (from Heraus) at 40° C. To this end, 5 g/l of a bleach-free base detergent (WMP, WFK, Krefeld) and 0.5 g/l of sodium perborate monohydrate (from Degussa) were dissolved in water of hardness level 3. Subsequently, 100 mg/l of activator were added. The wash time was 30 min. The bleached test fabric used was curry, ketchup and tea on cotton (BC-4, 10T and BC-1, WFK Testgewebe GmbH, Krefeld). The bleaching result was assessed as the difference in reflectance, measured with an Elrepho unit, after the wash in comparison to the unwashed fabric.

Difference in reflectance (dR %)

Activator BC-4 10T BC-1

Cyanomethyltrimethylammonium 62.1 74.7 55.1

tosylate

Cyanomethyldiethylmethylammonium 62.9 75.2 54.9

tosylate
It can be seen that the inventive bleach activator (prepared according to Example 3) has a comparable bleaching action to the prior art (cyano-methyltrimethylammonium tosylate, prepared by reaction of dimethylamino-acetonitrile with methyl p-toluenesulfonate).
Essentially the same results were obtained when the sodium perborate was replaced with sodium percarbonate monohydrate.

Claims

1. A diethylmethylammonionitrile of the formula (1)

in which A is selected from the group consisting of chloride, bromide, sulfate, hydrogensulfate, methosulfonate, ethanesulfonate, toluenesulfonate, benzenesulfonate, and cumenesulfonate.

2. A washing and cleaning composition comprising a compound of the formula 2

in which A is an anion.

3. The washing and cleaning composition of claim 2, wherein the compound of the formula 2 is present in the form of a granule.

4. A process for bleaching colored stains on a textile and a hard surface, said process comprising contacting the textile or the hard surface with a solution comprising the diethylammonionitriles of the formula (2)

wherein A is an anion together with a peroxygen compound.

5. The process of claim 4, wherein the process is carried out at a bleaching temperature between 40 and 60° C.