EP0469018A1 - Copolymerizates based on monoethylenically unsaturated dicarboxylic acid anhydrides, diketens and monoethylenically unsaturated monocarboxylic acids, their production and use - Google Patents

Abstract

Copolymers containing in polymerized form as characteristic monomers (a) between 10 and 60 mol% of monoethylenically unsaturated biccarbonic acid anhydrides with 4 to 8 C atoms; (b) between 5 and 60 mol% of diketene; and (c) between 0.5 and 60 mol% of at least one monoethylenically unsaturated monocarbonic acid with between 3 and 8 C atoms. These copolymers, in their hydrolysed form, have K values between 15 and 120 (depending the method of H. Fikentscher, in an aqueous solution at 25 ° C, with a pH of 7, the concentration of the sodium salt in the copolymers being 2% by weight). The invention further relates to a process for the production of copolymers which consists in polymerizing monomers of groups (a), (b) and (c) in inert solvents, in the presence of polymerization stimulants, at relatively high temperatures. , and isolating the copolymers or, if necessary, subjecting them to solvolysis. These copolymers can be used as additives in liquid or powdered detergents, in an amount of 0.1 to 15% by weight.

Description

Copolymers based on monoethylenically unsaturated dicarboxylic anhydrides, diketene and monoethylenically unsaturated monocarboxylic acids, their preparation and use Description

Copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, such as maleic anhydride, diketene and C ₁ -C ₂₂ -alkyl vinyl ethers, are known from US Pat. No. 4,009,110. These copolymers can also. are in partially hydrolyzed form. The at least partially hydrolyzed copolymers are used, for example, as surface-active compounds, as glass cleaners or as builders for solid and liquid detergents. According to the information in the examples, the copolymers are used in amounts of 7.5 to 30% by weight in detergent formulations. The copolymers act as builders, prevent dirt from re-accumulating on the washed textiles when washing textile materials and have a certain calcium complex binding capacity.

EP-PS 00 25 551 discloses the use of copolymers of 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid or their alkali metal or ammonium salts as incrustation inhibitors in detergents. The copolymers are contained in amounts of 0.5 to 10% by weight. Although the copolymers are very effective incrustation inhibitors, it is not possible to prepare stable liquid detergent formulations with them, because a phase separation occurs after a relatively short time.

The present invention has for its object to provide improved polymeric additives for liquid and powder detergent formulations.

The object is achieved according to the invention with copolymers based on monoethylenically unsaturated dicarboxylic anhydrides and diketene if the copolymers are characteristic monomers

(a) 10 to 60 mol.% of monoethylenically unsaturated dicarboxylic anhydrides with 4 to 8 carbon atoms,

(b) 5 to 60 mole percent diketene,

(c) 0.5 to 60 mol% of at least one monoethylenically unsaturated C ₃ to C ₈ monocarboxylic acid and (d) contain 0 to 20 mol.% of other monoethylenically unsaturated comonomers copolymerizable with the monomers (a) to (c) and in the hydrolyzed form have K values of 15 to 120 (determined by H. Fikentscher in aqueous solution) 25 ° C, pH 7 and a concentration of the sodium salt of the copolymers of 2% by weight). The copolymers can be prepared by

(a) 10 to 60 mol.% of monoethylenically unsaturated dicarboxylic anhydrides with 4 to 8 carbon atoms,

(b) 5 to 60 mole percent diketene,

(c) 0.5 to 60 mol% of at least one monoethylenically unsaturated C ₃ to C ₈ monocarboxylic acid and

(d) 0 to 20 mol% other, with the monomers (a) to (c)

 copolymerizable monomer mixtures containing monoolefinically unsaturated comonomers are copolymerized in a solvent which is inert to the monomers in the presence of polymerization initiators at from 40 to 160 ° C. and the copolymers are isolated or the anhydride and ketene groups of the copolymers are hydrolyzed, if appropriate. Component a) of the copolymers are monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 8 carbon atoms, e.g. Maleic anhydride, itaconic anhydride, mesaconic anhydride, citraconic anhydride and methylene malonic anhydride. Of the anhydrides mentioned, maleic anhydride and itaconic anhydride are preferably used, maleic anhydride being of particular importance in practice. The copolymers contain 10 to 60, preferably 20 to 50 mol.% Of at least one of the dicarboxylic acid anhydrides mentioned in polymerized form.

The copolymers contain as component b) 5 to 60, preferably 10 to 40, mol% of diketene copolymerized.

As a further essential constituent, the copolymers contain, as component (c), at least one monoethylenically unsaturated C ₃ - to C ₈ -monocarboxylic acid polymerized in, for example acrylic acid, methacrylic acid, vinyl acetic acid, allylacetic acid, propylidene acetic acid, ethylidene acetic acid, crotonic acid, α, β-ethyl acrylic acid and α, β -Dimethylacrylic acid. From this group of monomers, acrylic acid and methacrylic acid are preferably used. Insofar as anhydrides are accessible from these carboxylic acids, for example Methacrylic anhydride and acrylic anhydride, these anhydrides can also be used in the copolymerization. The monomers of group c) make up 0.5 to 60, preferably 5 to 50, mol% of the copolymers. The preparation of copolymers which are particularly preferred

(a) 20 to 50 mol% maleic anhydride,

(b) 10 to 40 mole percent diketene and

(c) contain 5 to 50 mol.% of acrylic acid, methacrylic acid or mixtures of acrylic acid and methacrylic acid in copolymerized form.

A further modification of the copolymers can be achieved by copolymerization in the presence of monomers

Group (d) carries out. These include other monoethylenically unsaturated monomers that are different from the monomers of groups (a), (b) and (c). For example, for this purpose, acrylamide, methacrylamide, di- suitable methylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrolein, methacrolein, Vinylester of C ₁ - to C ₂₀ saturated carboxylic acids, in particular vinyl acetate and vinyl propionate, alkyl vinyl ether with C ₁ - to C ₄ -alkyl groups, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether and isobutyl vinyl ether, methacrylic acid and acrylic acid alkyl esters of C ₁ - to C ₈ -alcohols, for example methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, 2-ethyl-2-ethylhexyl acrylate methacrylate, methyl methacrylate, methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate and isobutyl methacrylate, N-vinyl pyrrolidone, N-vinyl amides, such as N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole, N-vinyl imidazoline, N-vinyl vinyl Methylimidazole in. The basic monomers k can be used in the form of the free bases as well as in neutralized or quaternized form in the copolymerization. The monomers of group (d) are involved in the synthesis of the copolymers from 0 to 20 mol%.

The copolymerization takes place in inert organic solvents which practically do not interfere with the polymerization and which do not react with the monomers. Such solvents are, for example, C ₃ bis

Cio-ketones such as acetone, diethyl ketone, methylethyl lketon and cyclohexanone, ethers such as tetrahydrofuran and dioxane, esters of saturated C ₂ - to C ₄ -carboxylic acids and saturated monohydric C ₁ - to C ₄ alcohols such as methyl acetate, ethyl acetate, isopropyl acetate , Methyl propionate, ethyl propionate, isobutyl propionate, methyl butyrate, Butyrate and Buttersäureisobutylester, aromatic hydrocarbons such as benzene, toluene, xylene and cumene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane and diethylcyclohexane, halogenated aliphatic hydrocarbons, such as methylene chloride, dichloroethane, trichloroethane and tetrachloroethane and carbon dioxide. If the polymerization is carried out in carbon dioxide, it takes place at temperatures above 31 ° C. in supercritical carbon dioxide. Acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, toluene or xylene are preferably used as solvents. The polymerization can of course also be carried out in mixtures of inert solvents which do not react with the anhydride groups of the monomers or polymers.

The copolymerization takes place in the presence of compounds which break down into free radicals under the polymerization conditions. Suitable polymerization initiators are, for example, hydrogen peroxide, organic peroxides and hydroperoxides, peroxydisulfates, redox initiators and starters. The polymerization can also be carried out by exposure to high-energy radiation or by irradiation of the reaction mixture in the presence of a

Photoinitiators, such as benzoin, can be made.

The initiators should preferably have a half-life of <3 hours at the chosen polymerization temperatures. If, for example, polymerization is carried out at a low temperature and polymerization is carried out at a higher temperature, it is advisable to work with at least 2 initiators. For example, the following initiators are suitable for the polymerization temperatures mentioned:

Temp.: 50 to 60 ° C:

Acetylcyclohexanesulfonyl peroxide, dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl perneodecanoate, 2,2'-azobis- (4-methoxy-2,4-dimethy1-valeronitrile)

Temp .: 70 to 80 ° C:

tert-butyl perpivalate, dioctanoyl peroxide, dilauryl peroxide,

2,2'-azobis (2,4-dimethylvaleronitrile)

Temp .: 90 to 100 ° C:

tert-butyl per-2-ethylhexanoate

Temp .: 110 to 120 ° C:

Bis (tert-butylperoxy) cyclohexane, tert-butylperoxyisopropyl carbonate, tert-butylperacetate Temp.: 130 to 140 ° C:

 2,2-bis (tert-butylperoxy) butane, dicumyl peroxide, di-tert-amyl peroxide,

Di-tert-butyl peroxide temp .: 150 ° C:

p-menthane hydroperoxide, pinane hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide.

By using redox coinitiators such as benzoin or dimethylani 1 in and organically soluble complexes or salts of heavy metals such as copper, cobalt, manganese, iron, nickel, chromium, the half-lives of the peroxides mentioned, especially the hydroperoxides, can be reduced , so that, for example, tert-butyl hydroperoxide is effective at 100 ° C. in the presence of 5 ppm copper (II) acety lacetonate.

The free radical polymerization initiators are used in conventional amounts, e.g. 0.1 to 5 wt.%, Based on the at

Polymerization used amounts of monomers.

The copolymerization can optionally be carried out in the presence of customary regulators, for example thio and mercapto compounds such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, thiolactic acid, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan and dodecyl mercaptan. Other suitable regulators are aldehydes, such as acetaldehyde, propionaldehyde and butyraldehyde and formic acid. Provided that they are used in the polymerization, the regulators are used in amounts of 0.01 to 2%. The copolymerization can optionally be carried out in the presence of crosslinking agents. Suitable crosslinkers are, for example, ethylene glycol divinyl ether, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate, butanediol-1,4-diacrylate, butane-1,4-dimethacrylate, hexanediol-1, 6-dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate and acrylic acid or methacrylic acid esters of alcohols with more than 2 hydroxyl groups, eg trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. Also suitable are diacrylates and dimethacrylates of polyethylene glycols or polypropylene glycols with molecular weights which are preferably in the range from about 400 to 2000. The di-, trimaleinates and (meth) acrylate maleinates corresponding to the above di- and tri (meth) acrylates can also be used as crosslinkers. If the copolymerization is carried out in the presence of crosslinking agents, then the amount of crosslinker is 0.1 to 2.5% by weight, based on the total monomers used in the copolymerization.

The polymerization is preferably carried out in stirred tanks, which are equipped, for example, with an anchor, blade or impeller stirrer. The copolymerization can be carried out, for example, as a solution, precipitation or suspension polymerization. In the case of precipitation and suspension polymerization, it may be advantageous to additionally polymerize in the presence of protective colloids. Suitable protective colloids are, for example, copolymers of maleic anhydride with vinyl alkyl ethers which contain 1 to 20 carbon atoms in the alkyl group, or copolymers of maleic anhydride and olefins with 8 to 20 carbon atoms and their monoesters with C ₁₁ -C ₂₀ alcohols or monoamides with C ₁₀ bis C ₂₀ amines. Also suitable are polyalkyl vinyl ethers whose alkyl group contains 1 to 20 carbon atoms, for example polymethyl, polyethyl and polyisobutyl vinyl ether. If a protective colloid is used in the copolymerization, the effective amounts are 0.05 to 4% by weight, based on the monomers to be polymerized. The concentration of the monomers in the inert organic solvents is 5 to 70, preferably 15 to 50% by weight. The polymerization temperature is in the range from 40 to 160, preferably 50 to 150 ° C. After the copolymerization has ended, the copolymers can be isolated, for example by distilling off the solvent used in the polymerization or by precipitating the polymers with a suitable solvent. The copolymers then remain as a powdery residue. Since the copolymers contain reactive groups such as anhydride and β-lactone groups, they are sensitive to moisture. When they are brought into contact with water, they hydrolyze easily, two carboxyl groups being formed from each anhydride group and the β-lactone unit contained in the copolymer reacting with water according to the following reaction scheme

The reactive groups in the copolymer, in particular the anhydride and β-lactone groups, can not only be hydrolyzed with water, but can also be reacted with alcohols, primary or secondary amines. Hydrolysis, ie the action of water on the copolymer produced, gives rise to water-soluble copolymers which are water-soluble at least in the form of the alkali metal and ammonium salts. The anhydride and β-lactone groups of the copolymers can be reacted in the organic solvent in which the copolymerization was carried out or the solvents used are first distilled off and then the hydrolysis of the ketene and anhydride groups or their reaction with alcohols or amines is carried out by. The one in hydrolysis

resulting aqueous solutions of carboxyl-containing

Copolymers can be used directly as detergent additives.

If the copolymers in the form of the free acids are not sufficiently soluble in water, they can be used in partially or completely neutralized form. For partial or

complete neutralization of the copolymers, preferably sodium hydroxide solution, potassium hydroxide solution, ammonia or alkanolamines, e.g. Ethanolamine, diethanolamine, triethanolamine or mixtures of the bases mentioned. The copolymers are water-soluble, at least in neutralized form and, in the hydrolyzed form, have K values of 15 to 120, preferably 20 to 80 (determined in aqueous solution at pH 7 on the sodium salt of the

Copolymers at 25 ° C and a polymer concentration of 2 wt.%). However, the non-hydrolyzed copolymers can also be partially esterified by reaction with alcohols, a carboxyl and an ester group being formed from an anhydride group in the polymer in the reaction with an alcohol, and a β-hydroxycarboxylic acid ester being formed from a β-lactone unit in the copolymer. Suitable alcohols are, for example, C ₁ -C ₃₀ -alcohols or, particularly advantageously, those compounds containing OH groups which are obtained by reacting

(A) C ₁ to C ₃₀ alcohols, C ₈ to C ₂₂ fatty acids, C ₁ to C ₁₂ alkyl phenols, secondary C ₂ to C ₃₀ amines or mixtures thereof

(B) at least one C ₂ - to C ₄ -alkylene oxide in the molar ratio (A): (B) of 1: 2 to 50 can be produced. Suitable compounds (A) are C ₁ to C ₃₀ alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, cyclohexanol, n-hexanol, n-octanol, 2 -Ethylhexanol, decanol, dodecanol and stearyl alcohol. The alcohols produced by the oxo process, for example C ₁₀ alcohols, are of particular technical importance.

C ₁₃ alcohols and C ₁₃ / C ₁₅ alcohols or also native alcohols, such as, for example

C ₁₆ / C ₁₈ tallow fatty alcohols. The alcohols produced by the oxo process and the native alcohols are generally mixtures of several alcohols. Suitable compounds (A) are also C ₈ to C ₂₂ fatty acids, for example

Stearic acid, palmitic acid, coconut fatty acid, tallow fatty acid and lauric acid. Also suitable as component (A) are C ₁ -C ₁₂ -alkylphenols, for example n-decylphenol, n-nonylphenol, isononylphenol, n-octylphenol, isobutylphenol and methylphenol. Secondary C ₂ - to C ₃₀ -amines are also used as component (A), for example dimethylamine, di-n-butylamine, di-n-octylamine and di-stearylamine. Secondary C ₈ to C ₁₈ fatty amines are preferably used. Preferred as component (A) are C ₁ - bis

C ₃₀ ~ alcohols or sec. C ₂ - to C ₁₈ amines used.

Suitable components (B) are C ₂ -C 4 -alkylene oxides, for example ethylene oxide, propylene oxide, n-butylene oxide and isobutylene oxide. Tetrahydrofuran can also be used as component (B). Preferred for use

Compounds (B) obtained are ethylene oxide and propylene oxide. Ethylene oxide and propylene oxide can be used either alone on those specified under (A)

Compounds are added or in the form of a mixed gas with the formation of adducts containing randomly structured ethylene oxide and propylene oxide units, or else in such a way that ethylene oxide and then propylene oxide are first added to the compounds mentioned under (A) or the order is reversed or else ethylene oxide first, then propylene oxide and again ethylene oxide are added to the compounds (A), so that block copolymers are formed. Process for the alkoxylation of

Compounds (A) belong to the prior art. The compounds (A) are combined with the compounds (B) in one

 Molar ratio of (A) to (B) from 1: 2 to 50, preferably 1: 3 to 12 implemented. This reaction results in all cases in reaction products in which at least one end group is an OH group. The reaction products from (A) and (B) thus produced are reacted with the unhydrolyzed copolymers described above, partially esterified copolymers being formed. This reaction can be carried out in the presence of solvents inert to carboxylic anhydride groups, e.g. Acetone or tetrahydrofuran, and will be carried out

preferably done in bulk, i.e. the copolymers containing dicarboxylic acid anhydride groups are reacted directly with the reaction products of (A) and (B). The amounts are chosen so that only partial esterification of the ketene and anhydride groups occurs. Based on the hydrolyzed partially esterified

Copolymer more than 5, for example 5.5 to 50, preferably 9 to 30% of the total carboxyl groups present are esterified. The esterification itself is generally carried out at higher temperatures, for example 50 to 200, preferably 80 to 150 ° C. in the presence of conventional esterification catalysts. P-Toluenesulfonic acid is particularly suitable as a catalyst. The esterification reaction is after about 0.5 to 20, preferably 1 to 10 hours ended. The partial esterification of the unhydrolyzed copolymers with the reaction products from (A) and (B) leads to products which allow the production of particularly stable storage liquid detergent formulations. Such products are also obtained if the reaction of the non-hydrolyzed copolymers is carried out with long-chain primary amines, for example C ₁₀ -C ₂₂ -alkylamines or amines of the

formula

in which the substitutes ten

R ¹ = C ₈ - to C ₂₈ -Alky,

RO-

R = C ₁ to C ₂₈ alkyl, H

R ³ , R ⁴ = H, CH ₃ , C ₂ H ₅ ,

n = 2 to 100, and

R ^{2 is} H or R ¹ . In this reaction, the anhydride groups of the copolymers are converted into the corresponding half-amide groups, and β-hydroxycarboxamides are formed from the ketene groups. Since the non-hydrolyzed copolymers, which contain units of compounds of groups (a), (b) and (c) in copolymerized form as essential constituents, are only partially reacted with alcohols or amines, the anhydride components still present in the copolymer after the reaction are hydrolyzed. and ketene groups. The copolymers thus obtainable can then be partially or completely neutralized with the bases specified above. The hydrolysis can of course also be carried out with the aid of aqueous bases, for example aqueous sodium hydroxide solution.

When the copolymers are neutralized, yellow or orange colored products are obtained with a high proportion of diketene in the polymer. Complete decolorization is achieved by post-treatment with an oxidizing agent, preferably hydrogen peroxide, using 1 to 30 mol% of the oxidizing agent, preferably 2 to 15 mol% hydrogen peroxide become. The oxidizing agent can be added during the neutralization or afterwards at temperatures between 10 and 120 ° C., preferably between 50 and 100 ° C. The copolymers can be used either in the non-hydrolyzed form or in the form of the aqueous solution or in the form of a powder. When the products to be used according to the invention are used in liquid detergents, the starting point is preferably aqueous solutions of the copolymers. Such solutions can of course also for

Production of powder detergents can be used by drying these solutions or by applying them to powder constituents of the detergent formulation and drying them. The liquid detergents and the powder detergent formulations each contain 0 to 15, preferably 0.5 to 10% by weight of at least one copolymer of the composition described above. The detergent formulations contain essential components

(1) at least one anionic surfactant, a nonionic surfactant or

 their mixtures and

(2) a copolymer to be used according to the invention.

Water-based and water-free liquid detergents can be used, which can be clear or cloudy. If the polymers according to the invention are insoluble in the liquid detergent formulation, the copolymers can also be finely divided and, if necessary, stabilized with dispersants. Suitable anionic surfactants in liquid detergents are, for example, sodium alkylbenzenesulfonates, fatty alcohol sulfates and fatty alcohol polyglycol ether sulfates. Individual compounds of this type are, for example, C ₈ - to C ₁₂ -alkylbenzenesulfonates, C ₁₂ - to C ₁₆ -alkanesulfonates, C ₁₂ - to C ₁₆ -alkyl sulfates, C ₁₂ - to C ₁₆ -alkylsulfosuccinates and sulfated ethoxylated C ₁₂ - bis C ₁₆ alkanols. Also suitable as anionic surfactants are sulfated fatty acid alkanolamines, fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols. Other suitable anionic surfactants are fatty acid esters or fatty acid amides of hydroxy or amino carboxylic acids or sulfonic acids, such as, for example, the fatty acid sarcosides, glycolates, lactates, taurides or isothionates. The anionic surfactants can be present in the form of the sodium, potassium and ammonium salts and as soluble salts, organic bases, such as mono-, di- or triethanolamine or other substituted amines. The anionic surfactants also include the usual soaps, ie the alkali salts of the natural fatty acids. Addition products of 3 to 40, preferably 4 to 20 moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkane sulfonamide can be used, for example, as nonionic surfactants (nonionics). The addition products of 5 to 16 moles of ethylene oxide with coconut or tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in are particularly important the alkyl residues. In addition to these water-soluble nonionics, non-fully or not completely water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.

Furthermore, the non-ionic surfactants that can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol ether, alkylene diaminopolypropylene glycol and alkyl polypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol ether chain functions as a hydrophobic residue. Nonionic surfactants of the amine oxide or sulfoxide type can also be used.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants. A reduction can also be achieved by adding non-surfactant-like organic substances.

The liquid, aqueous detergents contain 4 to 50% by weight of surfactants. You can contain an anionic or nonionic surfactant in the amount specified. However, it is also possible to use mixtures of anionic and nonionic surfactants. In such a case, the content of anionic surfactants in the liquid detergent is selected from 0 to 50% by weight and the content of nonionic surfactants in the liquid detergent from 0 to 50% by weight, based on the total detergent formulation. The liquid detergents can contain water in amounts of 10 to 60, preferably 20 to 50,% by weight. But they can also be anhydrous.

The liquid detergents may also contain other substances for modification. These include, for example, alcohols, such as ethanol, n-propanol and isopropanol, and low molecular weight polyalkylene oxides, such as di-, tri- and tetraethylene glycol or corresponding propylene glycols. If they are used, these substances are used in amounts of 0.1 to 15% by weight, based on the total detergent formulation. used. Anhydrous liquid detergents can also contain peroxy compounds for bleaching in suspended or dispersed form. The following may be mentioned as peroxo compounds: sodium perborate, perosocarboxylic acids and polymers with partially peroxo-containing groups. The liquid detergents may also contain hydrotropes. This includes compounds such as 1,2-propanediol, cumene sulfonate and toluene sulfonate. If such compounds are used to modify the liquid detergent, their amount, based on the total weight of the liquid detergent, is 2 to 5% by weight. In many cases, the addition of complexing agents has also proven to be advantageous for modifying powdery and liquid detergents. Complexing agents are, for example, ethylenediaminetetraacetic acid, nitrilotriacetate and isoserinediacetic acid, and phosphates, such as aminotrismethylenephosphonic acid, hydroxyethanephosphonic acid, ethylenediaminetetraethylenephosphonic acid and their salts. The complexing agents are used in amounts of 0 to 10% by weight, based on the detergents. The detergents can also contain citrates, di- or triethanolamine, opacifiers, optical brighteners, enzymes, perfume oils and dyes. If these substances are used to modify the liquid detergents, they are present together in amounts of up to 5% by weight. The detergents are preferably phosphate-free. However, they can also contain phosphates, for example pentasodium triphosphate and / or tetrakai iumpyrophosphate. If phosphates are used, the proportion of the phosphates in the total formulation of the detergent is 10 to 25% by weight. Powder detergents can have different compositions.

The registered compounds can also be combined with other known detergent additives (such as incrustation inhibitors, graying inhibitors, clay dispersants and substances that enhance the primary washing action, color transfer inhibitors, bleach activators) in powder and

Liquid detergents (phosphate-free and phosphate-free) produce synergistic effects in which not only the incrustation inhibition but also the effect of the other detergent additive can be enhanced. Detergent additives are to be understood here as meaning substances which are used in amounts of up to 15% by weight, based on the detergent formulation, and which have one or more advantageous washing properties. Universal household detergents for drum washing machines, as are widespread in Europe, usually contain 5 to 10% by weight of anionic surfactants; 1 to 5% by weight of nonionic surfactants; 1 to 5% by weight of foam regulators, such as silicone oils or soaps; 0 to 40 wt .-% softening agents such as soda or Pentasodium triphosphate, which can be partially or completely replaced by the compounds according to the invention; 0 to 30% by weight of ion exchangers, such as zeolite, bentonites, such as, for example, ZeoLith A; 2 to 7% by weight sodium silicates as corrosion inhibitors; 10 to 30% by weight of bleaching agents, such as sodium perborate or sodium percarbonate; 0 to 5 wt .-% bleach activators, such as

Tetraacetylethylene diamine, pentaacetyl glucose, hexaacetyl sorbitol or acyloxybenzenesulfonate; Stabilizers, such as magnesium silicate or ethylenediaminetetraacetate; Graying inhibitors, such as carboxymethyl cellulose, methyl and hydroxyalkyl celluloses, polyglycols grafted with vinyl acetate, oligomeric and polymeric terephthalic acid / ethylene glycol / polyethylene glycol esters; Enzymes; optical brighteners; Fragrances; Dyes and fillers. In contrast to this, the heavy duty detergents used in the tub washing machines in the United States, Japan and these countries are mostly free of bleach, their proportion of anionic surfactants is two to three times as high, they contain more washing alkalis, like soda and sodium silicates (usually up to

25% by weight) and of course they also lack the bleach activators and bleach stabilizers. The content of surfactants and other ingredients can increase considerably if it is a matter of so-called detergent concentrates, which are sold on a retail basis without the use of adjuvants or with no additives. Mild and colored detergents; Wool detergents and agents for manual washing usually also contain no bleach and low alkaline components with a correspondingly high proportion of surfactants. Detergents for the commercial sector are tailored to the specific ratios of industrial washing (soft water, continuous washing), which make it possible to focus on the type of laundry and soiling. Combinations are therefore used in which one component predominates or others are completely absent, which are added separately if necessary. Therefore, the ingredients surfactants, builders (builders), alkalis and bleaches of these detergents vary within wide limits. Suitable anionic and nonionic surfactants for powder detergents are the same as those mentioned under liquid detergents.

The percentages in the examples are% by weight. The K values were determined according to H. Fikentscher, Cellulosechemie, Vol. 13, 58 to 64 and 71 to 74 (1932); where K = k. 103. The K values of the hydrolyzed copolymers were measured in aqueous solution at 25 ° C., a pH of 7.0 and a polymer concentration of 2% by weight of the sodium salts of the copolymers. Examples 1 to 5

350 ml of toluene and the in are placed in a glass reactor which is provided with a stirrer and three feeds and is flushed with nitrogen

 Amounts of maleic anhydride indicated in Table 1 and the solution is heated to 80 ° C. with stirring. As soon as the specified temperature has been reached, the amounts of acrylic acid and diketene, which are also shown in Table 1 and are each dissolved in 50 ml of toluene, are added within 2 hours. Together with the addition of the monomers, a solution of 4.46 g of tert-butyl perpi valate (75% in al-ipatic hydrocarbons) in 50 ml of toluene is metered in over the course of 2.5 hours. After the initiator addition has ended, the reaction mixture is stirred for a further 3 hours at 80 ° C., then 300 g of water are added and the mixture is adjusted to a pH of 6.5 while cooling with 150 g of a 50% strength aqueous sodium hydroxide solution. The copolymers are then each precipitated by adding a mixture of acetone and methanol in a weight ratio of 1: 1 and dried at 75 ° C. in vacuo. The products are colored yellow and have the K values given in Table 1. Examples 6 to 8

In a glass reactor equipped with a stirrer, three feeds and a device for working under nitrogen, 280 ml of toluene and the amounts of maleic anhydride given in each case in Table 1 are placed and heated to a temperature of 80 ° C. with stirring . As soon as the specified temperature is reached, the in

Amounts of diketene given in Table 1, which is dissolved in 50 ml of toluene, and acrylic acid are added in each case. Starting with the addition of monomers, a solution of 4.2 g of tert-butyl perpivalate (75% in al-ipatic hydrocarbons) in 50 ml of toluene is added to the reaction mixture within 2.5 hours. After the initiator addition has ended, the reaction mixture is stirred for a further 3 hours at 80 ° C., then 300 g of water are added and, with cooling, 150 g of a 50% strength aqueous solution

Sodium hydroxide solution adjusted to a pH of 6.5. The copolymer is then by adding a mixture of acetone and methanol in

Weight ratio 1: 1 precipitated and dried at a temperature of 75 ° C in a vacuum. The copolymers obtained are colored yellow and have the K values given in Table 1. Example 9

In a glass reactor equipped with a stirrer, three inlets and a device for working under nitrogen, who the 280 ml of methyl ethyl ketone and the amount of maleic anhydride given in Table 1 and heated to a temperature of 70 ° C with stirring. As soon as the temperature of 75 ° C is reached, the amount of acrylic acid and methylene shown in Table 1 is added within 1.5 hours. Simultaneously with the addition of monomers, a solution of 4.9 g of tert-butyl perpi valate (75% in al-ipatic hydrocarbons) in 50 ml of methyl ethyl ketone is metered into the reaction mixture within 2 hours. After the initiator addition has ended, the reaction mixture is stirred at 80 ° C. for a further 2 hours. The solvent is then distilled off in vacuo and the copolymer is hydrolyzed by adding aqueous sodium hydroxide solution and adjusted to a pH of 7. In order to isolate the polysodium salt of the copolymer, a mixture of acetone and methanol in a weight ratio of 1: 1 is added to the aqueous solution, so that the salt of the copolymer precipitates. The K value of the copolymer is 24.5 under the conditions specified above.

Example 10

Example 4 is repeated with the exception that instead of

Acrylic acid uses 0.7 moles of methacrylic acid. A copolymer with a K value of 26.9 is obtained.

Example 11 Example 4 is repeated with the exception that 40 mol% of the

Acrylic acid replaced by vinyl acetate. The vinyl acetate was metered into the reaction mixture in a separate feed. The copolymer had a K value of 31.1. Example 12

Example 5 is repeated, the neutralization by adding

50% aqueous sodium hydroxide solution was carried out at 80 ° C. within 1 hour and 14.5 g of a 30% solution of hydrogen peroxide were simultaneously added. The reaction mixture was then stirred at 80 ° C. for 1 hour and then the polysodium salt of the copolymer was precipitated with a mixture of acetone and methanol in a weight ratio of 1: 1 and dried at 75 ° C. in vacuo. The polysodium salt of the copolymer was pale yellow and had a K value of 29.3. Example 13

Example 12 was repeated with the exception that 29 g of hydrogen peroxide (30% strength) were metered in during the neutralization. The polysodium salt of the copolymer obtained was colorless and had a K value of 28.5.

Example 14 Example 12 was repeated with the exception that 58 g of 30% hydrogen peroxide were used during the neutralization. The polysodium salt of the copolymer obtained was colorless and had a K value of 26.2.

 The following copolymers were tested for comparison with the prior art:

Copolymer 15

Copolymer of maleic anhydride, diketene and n-butyl vinyl ether in a molar ratio of 0.7: 1: 0.3 according to US Pat. No. 4,009,110, Example 3. Copolymer 16

 Copolymer of maleic anhydride and diketene in a molar ratio of 1: 1 according to DE-OS 23 42 300, example 1. Copolymer 17

 Copolymer of maleic acid and acrylic acid in a weight ratio of 70:30 according to EP-PS 00 25-551.

Application engineering examples

In order to test the incrustation-inhibiting effect of the hydrolyzed copolymers described above, the copolymers described above were each incorporated into two different powder detergents A and B. Test fabrics made of cotton and cotton terry cloth were washed with these detergent formulations. The number of wash cycles was 15. After this number of washes, the ash content of the fabric was determined by ashing the test fabric in each case. The ash content is given in% by weight. The more effective the copolymer contained in the detergent, the lower the ash content of the test fabric.

Test conditions for determining the incrustation:

Device: Launder-O-Meter from Atlas, Chicago

Number of wash cycles: 20

 Wash liquor: 250 g, the water used has 4 mmol hardness per liter (molar ratio:

 Calcium to magnesium equal to 4: 1)

Washing time: 30 min. At 60 ° C (including heating up time) Detergent dosage: 8 g / 1

Fleet ratio 1: 12.5

Test fabric 10 g each

Detergent A

12.5% dodecylbenzenesulfonate (50%)

 4.7% C 13 / C 15 oxo alcohol polyglycol ether (7 EO)

 2.8% soap

25% zeolite A

 4% Na disilicate

 1% Mg silicate

20% sodium perborate 14% sodium sulfate

10% copolymerization

Balance on 100% sodium sulfate detergent B

12.5% dodecylbenzenesulfonate (50%)

 4.7% C 13 / C 15 oxo alcohol polyglycol ether (7 EO)

 2.8% soap

10% pentasodium triphosphate

 24% zeolite A

 6% Na disilicate

 1% Mg silicate

 20% sodium perborate

15% sodium sulfate

 3% copolymer

 Balance on 100% sodium sulfate

The products produced in Examples 1 to 14 were tested as copolymers 1 to 14 in detergent formulations A and B in accordance with the test conditions given above. The results given in Table 2 were obtained.

Claims

Claims

1. Copolymers based on monoethylenically unsaturated dicarboxylic anhydrides and diketene, characterized in that they are characteristic monomers

(a) 10 to 60 mol.% of monoethylenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms, (b) 5 to 60 mol.% of diketene,

(c) 0.5 to 60 mol% of at least one monoethylenically unsaturated C ₃ to C ₈ monocarboxylic acid and (d) 0 to 20 mol% of other, with the monomers (a) to (c)

 contain copolymerizable monoethylenically unsaturated comonomers in copolymerized form and in the hydrolyzed form have K values from 15 to 120 (determined according to H. Fikentscher in aqueous solution at 25 ° C., pH 7 and a concentration of the sodium salt of the copolymers of 2% by weight).

2. A process for the preparation of copolymers according to claim 1, characterized in that

(a) 10 to 60 mol.% of monoethylenically unsaturated dicarboxylic anhydrides with 4 to 8 carbon atoms,

(b) 5 to 60 mole percent diketene,

(c) 0.5 to 60 mol% of at least one monoethylenically unsaturated C ₃ to C ₈ monocarboxylic acid and

(d) 0 to 20 mol% other, with the monomers (a) to (c)

 copolymerizable monoethylenically unsaturated comonomers containing Monomergemi see in a solvent inert to the monomers in the presence of polymerization initiators copolymerized at 40 to 160 ° C and the copolymers isolated or the

 Anhydride and ketene groups of the copolymers, if appropriate

hydrolyzed.

3. The method according to claim 2, characterized in that (a) 20 to 50 mol.% Maleic anhydride, (b) 10 to 40 mol.% Diketene and

(c) 5 to 50 mol% acrylic acid, methacrylic acid or mixtures of

 Monomergemi containing acrylic acid and methacrylic acid see copolymerized.

4. The method according to claim 2 or 3, characterized in that the copolymers containing anhydride and ketene groups are reacted with alcohols, primary or secondary amines.

5. Use of the copolymers obtainable according to claims 2 and 4 as an additive to powdery or liquid detergents and cleaning agents in amounts of 0.1 to 15% by weight, based on the detergent formulations.