Detergents containing water-soluble copolymers containing as copolymerized units monomers having two or more ethylenically unsaturated double bonds

It is common knowledge that detergents must contain builders, as well as surfactants. Builders are required to perform many functions in detergent formulations; for instance, they are supposed to support the surfactants in soil detachment, deactivate the water hardness formers, whether by sequestration of alkaline earth metal ions or by dispersal of hardness formers precipitated from the water, augment the dispersal and stabilization of the soil colloidally distributed in the washing liquor, and act as buffers to maintain an optimum wash pH. In solid detergent formulations, builders are supposed to make a positive contribution to good powder structure and flowability. Builders which are based on phosphate meet the above-described requirements to a high degree. For instance, for a long time pentasodium triphosphate was indisputably the most important builder in detergents. However, the phosphates present in detergents pass virtually unchanged into the effluent. Since phosphates are a good nutrient for water plants and algae, they are responsible for the eutrophication of seas and slow-flowing water courses. In water treatment plants without a tertiary treatment stage for specific precipitation of phosphates, they are not removed to a sufficient degree. There is therefore a long history of prior art concerned with replacing phosphate builders in detergents.
In the meantime, for instance, water-soluble ion exchangers based on zeolites have found use in phosphate-free or low-phosphate detergents. However, owing to their specific properties zeolites alone cannot replace phosphates as builders. The action of zeolites is supported by the inclusion of other detergent additives comprising carboxyl-containing compounds, such as citric acid, tartaric acid, nitrilotriacetic acid and in particular polymeric carboxyl-containing compounds or salts thereof. Of the lastmentioned compounds, the homopolymers of acrylic acid and the copolymers of acrylic acid and maleic acid are of particular importance for use as detergent additives; cf. U.S. Pat. No. 3,308,067 and EP Pat. No. 25,551.
The polymers mentioned are ecologically safe since, in water treatment plants, they are adsorbed on the activated sludge and are removed together with the sludge from the water cycle. However, these polymers are not sufficiently biodegradable vis-a-vis the standards which effluent ingredients have to meet today.
It is an object of the present invention to provide additives for detergents based on polymers which, compared with the polymers hitherto used for this purpose, show a far better biodegradability.
We have found that this object is achieved according to the invention by using a water-soluble copolymer which contains
(a) from 99.5 to 15 mol % of one or more monoethylenically 20 unsaturated C.sub.3 - to C.sub.6 -monocarboxylic acids,
(b) from 0.5 to 20 mol % of one or more comonomers which
contain two or more ethylenically unsaturated nonconjugated double bonds and which have one or more --CO--OX groups where X is hydrogen, an alkali metal, one equivalent of an alkaline earth metal or ammonium,
(c) from 0 to 84.5 mol % of one or more comonomers which unsaturated C.sub.4 - to C.sub.6 -dicarboxylic acids,
(d) from 0 to 20 mol % of one or more hydroxyalkyl esters of from 2 to 6 carbon atoms in the hydroxyalkyl group of monoethylenically unsaturated C.sub.3 - to C.sub.6 -carboxylic acids and
(e) from 0 to 30 mol % of other water-soluble, monoethylenically unsaturated monomers copolymerizable with (a), (b), (c) and (d)
as copolymerized units, with the proviso that the sum of the mol % ages (a) to (e) is always 100, and which has a K value of from 8 to 120 (determined on the sodium salt by the Fikentscher method on a 1% strength by weight aqueous solution at 25.degree. C. and pH 7) as a detergent additive.
The copolymer described above acts as a builder in detergents and thus helps to boost the washing action of surfactants in the detergents, to reduce the incrustation on the washed textile material and to disperse the soil in the washing liquor. Compared with the polymers hitherto used in detergents, however, this copolymer is surprisingly biodegradable and in some instances even shows a better action.
The water-soluble copolymer is prepared by copolymerizing a monomer mixture of
(a) from 99.5 to 15 mol % of one or more monoethylenically unsaturated C.sub.3 - to C.sub.6 -monocarboxylic acids,
(b) from 0.5 to 20 mol % of one or more comonomers which contain two or more ethylenically unsaturated nonconjugated double bonds and which have one or more --CO--OX groups where X is hydrogen, an alkali metal, one equivalent of an alkaline earth metal or ammonium,
(c) from 0 to 84.5 mol % of one or more monoethylenically unsaturated C.sub.4 - to C.sub.6 -dicarboxylic acids,
(d) from 0 to 20 mol % of one or more hydroxyalkyl esters of from 2 to 6 carbon atoms in the hydroxyalkyl group of monoethylenically unsaturated C.sub.3 - to C.sub.6 -carboxylic acids and
(e) from 0 to 30 mol % of other water-soluble, monoethylenically unsaturated monomers copolymerizable with (a) to (d).
Above, the sum of the mol % ages (a) to (e) is always 100.
Component (a) of the water-soluble copolymer comprises monoethylenically unsaturated C.sub.3 - to C.sub.6 -monocarboxylic acids. Suitable carboxylic acids of this type are for example acrylic acid, methacrylic acid, ethacrylic acid, vinylacetic acid, allylacetic acid and crotonic acid. Preferably the monomer of component (a) is acrylic acid and/or methacrylic acid. The monomers of component (a) are involved in the buildup of the copolymer in a proportion of from 99.5 to 15 mol %.
An essential constituent of the copolymer comprises the monomers of component (b). They are comonomers which have two or more ethylenically unsaturated, nonconjugated double bonds and have one or more --CO--OH groups and/or salts with an alkali metal, ammonium or alkaline earth metal base. These comonomers in general bring about an increase in the molecular weight of the copolymer and are involved in the buildup of the copolymer in a proportion of from 0.5 to 20, preferably from 1 to 12, mol %.
The comonomers (b) are obtainable by reaction of
(b1) maleic anhydride, itaconic anhydride, citraconic anhydride or mixtures thereof with
(b2) polyhydric C.sub.2 - to C.sub.6 -alcohols, water-soluble or water-insoluble polyalkylene glycols having a molecular weight of up to about 400, water-soluble polyalkylene glycols having a molecular weight of from above about 400 to 10,000, polyglycerols having a molecular weight of up to 2,000, polyamines, polyalkylene polyamines, polyethyleneimines, amino alcohols, hydroxy-amino- or -diamino-carboxylic acids, in particular lysine and serine, copolymers of alkylene oxide and carbon dioxide, polyvinyl alcohol having a molecular weight of up to 10,000, allyl alcohol, allylamine, hydroxyalkyl esters having from 2 to 6 carbon atoms in the hydroxyalkyl group of monoethylenically unsaturated C.sub.3 - to C.sub.6 -carboxylic acids or saturated C.sub.3 - to C.sub.6 -hydroxycarboxylic acids or mixtures thereof.
Polyhydric C.sub.2 -C.sub.6 -alcohols are for example glycol, glycerol, pentaerythritol, sorbitol and monosaccharides, such as glucose, mannose, galactose, uronic acids, such as galacturonic acid, and saccharic acids, such as mucic acid or galactonic acid.
Water-soluble polyalkylene glycols refers to the addition products of ethylene oxide, propylene oxide, n-butylene oxide and isobutylene oxide or mixtures thereof on polyhydric alcohols having from 2 to 6 carbon atoms, for example the addition products of ethylene oxide on glycol, addition products of ethylene oxide on glycerol, addition products of ethylene oxide on pentaerythritol or sorbitol, addition products of ethylene oxide on monosaccharides and the addition products of mixtures of the alkylene oxides mentioned on polyhydric alcohols. These addition products may comprise block copolymers of ethylene oxide and propylene oxide, of ethylene oxide and butylene oxides or of ethylene oxide, propylene oxide and butylene oxides. Aside from the block copolymers it is also possible to use those addition products which contain the alkylene oxides mentioned as copolymerized units in random distribution. The molecular weight of the polyalkylene glycols is advantageously up to 5,000, preferably up to 2,000. Of the water-soluble polyethylene glycols, preference is given to using diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol having a molecular weight of up to 1,500.
Component (b2) can also comprise polyglycerols having a molecular weight of up to 2,000. Of this class of substances, preference is given to using diglycerol, triglycerol and tetraglycerol.
Suitable polyamines are for example preferably diamines, such as ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and 1,6-hexamethylenediamine, and melamine. Suitable polyalkylene polyamines are for example diethylenetriamine, triethylenetetramine, pentaethylenehexamine, N-(3-aminopropyl)-1,3-propanediamine and 3-(2-aminoethyl)aminopropylamine. Particularly suitable polyethylene imines have a molecular weight of up to 5,000.
Component (b2) can also be an amino alcohol, such as ethanolamine, 2-amino-1-propanol, neopentanolamine and 1-methylamino-2-propanol.
Suitable components (b2) also include copolymers of ethylene oxide and carbon dioxide which are obtainable by copolymerizing ethylene oxide and carbon dioxide. Also possible are polyvinyl alcohols having a molecular weight of up to 10,000, preferably up to 2,000. The polyvinyl alcohols, which are prepared by hydrolysis of polyvinyl acetate, can be completely or partially hydrolysed. Further suitable compounds of component (b2) are lysine, serine, allyl alcohol, allylamine and hydroxyalkyl esters having 2 to 6 carbon atoms in the hydroxyalkyl group of monoethylenically unsaturated C.sub.3 - to C.sub.6 -mono- and -dicarboxylic acids.
The hydroxyalkyl ester groups of the last monomers are derived from polyhydric alcohols, for example glycol, glycerol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, mixtures of butanediols or propanediols, 1,6-hexanediol and neopentylglycol. The polyhydric alcohols are esterified with monoethylenically unsaturated C.sub.3 -C.sub.6 -carboxylic acids. These comprise those carboxylic acids mentioned above under (a) and (c). A suitable component (b2) thus comprises for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxy-n-propyl methacrylate, hydroxy-n-propyl acrylate, hydroxyisopropyl acrylate, hydroxyisopropyl methacrylate, hydroxy-n-butyl acrylate, hydroxyisobutyl acrylate, hydroxy-n-butyl methacrylate, hydroxyisobutyl methacrylate, hydroxyethyl monomaleate, hydroxyethyl dimaleate, hydroxypropyl monomaleate, hydroxypropyl dimaleate, hydroxy-n-butyl monomaleate, hydroxy-n-butyl dmaleate and hydroxyethyl monoitaconate. Of the hydroxyalkyl esters of monoethylenically unsaturated dicarboxylic acids, not only the monoesters but also the diesters of said acids with the abovementioned polyhydric alcohols are possible.
Also suitable are hydroxyalkyl esters of saturated C.sub.3 -C.sub.6 -hydroxycarboxylic acids, such as glycol monohydroxy acetate, glycol monolactate and neopentylglycol hydroxypivalate.
Preference is given to using comonomers (b) from maleic anhydride and ethylene glycol, polyethylene glycol having a molecular weight of up to 2,000, glycerol, diglycerol, triglycerol, tetraglycerol, polyglycerols having a molecular weight of up to 2,000, pentaerythritol, monosaccharides, neopentyl glycol, .alpha.,.omega.-diamines of from 2 to 6 carbon atoms, .alpha.,.omega.-diols of from 3 to 6 carbon atoms, and neopentylglycol monohydroxypivalate. Comonomers (b) which are derived from ethylene glycol and .alpha.,.omega.-diols can be represented for example by means of the following formula: ##STR1## where X is H, an alkali metal or ammonium and
n is from 1 to 50.
Comonomers (b) which are formed by reacting maleic anhydride or maleic acid with .alpha.,.omega.-diamines can be characterized for example with the aid of the following formula ##STR2## where X is H, an alkali metal or ammonium and
n is from 0 to 4.
The monomer of component (c) is a monoethylenically unsaturated C.sub.4 - to C.sub.6 -dicarboxylic acid, for example maleic acid, itaconic acid, citraconic acid, mesaconic acid, fumaric acid or methylenemalonic acid. It is preferable to use maleic acid or itaconic acid as monomer (c). Monomer (c) is involved in the buildup of the copolymer in a proportion of from 0 to 84.5, preferably from 5 to 60, mol %.
The copolymer may contain hydroxyalkyl esters of from 2 to 6 carbon atoms in the hydroxyalkyl group of monoethylenically unsaturated C.sub.3 -C.sub.6 -carboxylic acids as copolymerized component (d) units. The hydroxyalkyl ester groups of this group of monomers are derived from polyhydric alcohols, for example glycol, glycerol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, mixtures of butanediols or propanediols, 1,6-hexanediol and neopentylglycol. The polyhydric alcohols are esterified with monoethylenically unsaturated C.sub.3 -C.sub.6 -carboxylic acids. These comprise those carboxylic acids mentioned above under (a) and (c). A suitable component (d) thus comprises for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxy-npropyl methacrylate, hydroxy-n-propyl acrylate, hydroxyisopropyl acrylate, hydroxyisopropyl methacrylate, hydroxy-n-butyl acrylate, hydroxyisobutyl acrylate, hydroxy-n-butyl methacrylate, hydroxyisobutyl methacrylate, hydroxyethyl monomaleate, hydroxyethyl dimaleate, hydroxypropyl monomaleate, hydroxypropyl dimaleate, hydroxy-n-butyl monomaleate, hydroxy-n-butyl dimaleate and hydroxyethyl monoitaconate. Of the hydroxyalkyl esters of monoethylenically unsaturated dicarboxylic acids, not only the monoesters but also the diesters of said acids with the abovementioned polyhydric alcohols are possible.
Preference is given to using as component ((d) hydroxyethyl acrylate, hydroxyethyl methacrylate, 1,4-butanediol monoacrylate, and the technical-grade mixtures of hydroxypropyl acrylates. Of these, there is a special interest in industry in the isomer mixtures of 2-hydroxy-1-propyl acrylate and 1-hydroxy-2-propyl acrylate. These hydroxyalkyl acrylates are prepared by reacting acrylic acid with propylene oxide. The monomers of group (d) are present in the copolymer in polymerized form in a proportion of from 0 to 20, preferably of from 0 to 15, mol %.
The copolymer may contain as component (e) other water-soluble monoethylenically unsaturated monomers copolymerizable with (a), (b), (c) and (d) Suitable monomers of this kind are for example acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, N-vinylimidazoline, 1-vinyl-2-methyl-2-imidazoline, vinyl acetate and mixtures thereof. Those monomers of this group which contain acid groups can be used in the copolymerization in the form of the free acids or else after partial or complete neutralization with alkali metal bases or ammonium bases. Basic acrylates, such as diethylaminoethyl acrylate, are neutralized or quaternized with acids and then subjected to the copolymerization. Monomer (e) is involved in the buildup of the copolymer in a proportion of from 0 to 30, preferably of from 0 to 20, mol %, merely serving to modify the copolymer.
The sum of the mol % ages of components (a) to (e) is always 100. The copolymerization is carried out in an aqueous medium, preferably in a purely aqueous medium. The copolymerization can take various forms; for example, monomers (a) to (e) can be polymerized batchwise in the form of aqueous solutions. It is also possible first to introduce initially into the polymerization reactor a portion of the monomers and a portion of the initiator, to heat the mixture in an inert gas atmosphere to the polymerization temperature, and then to add the other monomers and the initiator to the reactor at the rate of polymerization. The polymerization temperatures are within the range from 20.degree. to 200.degree. C. At above 100.degree. C., pressure vessels are employed. Preferably, the polymerization temperature is from 50.degree. to 150.degree. C.
In a preferred embodiment of the process of preparation, first comonomer (b) is prepared by
(b1) introducing maleic anhydride, itaconic anhydride, citraconic anhydride or mixtures thereof initially in a reactor and reacting it with
(b2) polyhydric C.sub.2 -C.sub.6 -alcohols, water-soluble or water-insoluble polyalkylene glycols having a molecular weight of up to about 400, water-soluble polyalkylene glycols having a molecular weight from above about 400 to 10,000, polyglycerols having a molecular weight of up to 2,000, diamines, polyalkylene polyamines, polyethyleneimines, amino alcohols, lysine, serine, copolymers of alkylene oxide and carbon dioxide, polyvinyl alcohol having a molecular weight of up to 10,000, allyl alcohol, allylamine, hydroxyalkyl esters of 2 to 6 carbon atoms in the hydroxyalkyl group of monoethylenically unsaturated C.sub.3 - to C.sub.6 -carboxylic acids or saturated C.sub.3 to C.sub.6 -hydroxycarboxylic acids or mixtures thereof
at from 50.degree. C. to 200.degree. C. This reaction is preferably carried out in the absence of water, although small amounts of water do not interfere if component (b1) is used in a corresponding excess. In place of the compounds mentioned under (b1), however, it is also possible to use the corresponding monoesters or diesters with C.sub.1 - to C.sub.4 -alcohols. In these cases a transesterification is carried out, and preferably the resulting C.sub.1 - to C.sub.4 -alcohol is distilled out of the reaction mixture. If amino-containing compounds as mentioned under (b2) are used, the reaction with the monoesters or diesters of the acid anhydrides of (b1) gives the corresponding amides. If, in the preparation of comonomers (b) esters of component (b1) are used, they preferably comprise dimethyl maleate, monomethyl maleate, dimethyl itaconate, monoisopropyl maleate and diisopropyl maleate. If desired, it is possible to use customary esterification catalysts.
Per mole of compound (b2), not less than 0.5 mole of a compound of component b1) is used. The temperature for the reaction is preferably from 50.degree. to 150.degree. C. The reaction is continued until conversion of component (b2) is virtually quantitative. Component (b1), which is customarily used in excess, can remain in the reaction mixture after the preparation of the comonomer has ended. In this case the comonomer can be dissolved in a monoethyleneically unsaturated C.sub.3 - to C.sub.6 -monocarboxylic acid as per (a) and then be subjected to copolymerization together with the unconverted portion of component (b1) and the other monomers. Since the copolymerization is carried out in an aqueous medium, excess dicarboxylic anhydride, (b1) still present in the comonomer is hydrolyzed to the corresponding dicarboxylic acid. This dicarboxylic acid is then to be considered a comonomer, (c).
However, initially prepared comonomer (b) which still contains excess dicarboxylic anhydride can also remain in the reaction mixture in which it was prepared and initially be dissolved therein by addition of water or dilute sodium hydroxide solution, which serves to hydrolyze the dicarboxylic anhydride still present. This monomer mixture is subsequently copolymerized by adding the other comonomers. The copolymerization of monomers (a) to (e) is carried out at a pH of the aqueous solution of from 2 to 9, preferably from 3 to 7. Monomers (a), (b) and (c), which each contain carboxylic acid groups, can be copolymerized in the form of the free carboxylic acids or a neutralized, preferably partially neutralized, form, the degree of neutralization being from 0 to 100, preferably from 40 to 90, mol %. The neutralization is preferably effected with alkali metal or ammonium bases. These include for example sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, potassium carbonate, ammonium bases such as ammonia, C.sub.1 -C.sub.18 -alkylamines, dialkylamines, such as dimethylamine, di-n-butylamine, dihexylamine, tertiary amines such as trimethylamine, triethylamine, tributylamine, triethanolamine and quaternized nitrogen bases, for example tetramethylammonium hydroxide, trimethyllaurylammonium hydroxide and trimethylbenzylammonium hydroxide. Neutralization is preferably effected with sodium hydroxide solution, potassium hydroxide solution or ammonia. However, the neutralization can also be effected with alkaline earth metal bases, for example calcium hydroxide or MgCO.sub.3.
The polymerization initiators used are preferably water-soluble free radical formers, for example hydrogen peroxide, peroxodisulfates and mixtures of hydrogen peroxide and peroxodisulfates. Suitable peroxodisulfates are for example lithium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate and ammonium peroxodisulfate. In mixtures of hydrogen peroxide and peroxodisulfate, it is possible to set any desired ratio; it is preferable to use hydrogen peroxide and peroxodisulfate in a weight ratio of from 3:1 to 1:3. Mixtures of hydrogen peroxide and sodium peroxodisulfate are preferably used in a weight ratio of 1:1. The abovementioned watersoluble polymerization initiators may also be used combined with reducing agents, for example iron(II) sulfate sodium sulfite, sodium hydrogensulfite, sodium dithionite, triethanolamine and ascorbic acid in the form of redox initiators. Suitable water-soluble organic peroxides are for example acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide and cumene hydroperoxide. They too can be used together with the abovementioned reducing agents. Further water-soluble polymerization initiators are azo starters, for example 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(N,N'-dimethylene)isobutyramidine dihydrochloride, 2-(carbamoylazoisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid). The polymerization can also be started with water-insoluble initiators, such as dibenzoyl peroxide, dicyclohexyl peroxodicarbonate, dilauryl peroxide or azodiisobutyronitrile.
The initiators are used in amounts of from 0.1 to 15, preferably from 0.5 to 10, % by weight, based on the sum of the monomers used in the polymerization. The polymerization initiators can be added to the mixture to be polymerized either together with the monomers or separately therefrom in the form of aqueous solutions either continuously or batchwise.
The copolymerization may also be carried out in the presence of regulants. Suitable for this purpose are preferably water-soluble compounds which either are miscible with water in any proportion or dissolve therein to more than 5% by weight at 20.degree. C. Compounds of this kind are for example aldehydes of from 1 to 4 carbon atoms, such as formaldehyde, acetaldehyde, propionaldehyde, nbutyraldehyde, isobutyraldehyde, formic acid, ammonium formate, hydroxylammonium salts, in particular hydroxylammonium sulfate, SH-containing compounds having up to 6 carbon atoms, such as thioglycolic acid, mercapto alcohols, such as mercaptoethanol, mercaptopropanol, mercaptobutanols, and mercaptohexanol, monohydric and polyhydric alcohols having up to 6 carbon atoms, such as isopropanol, glycol, glycerol and isobutanol. Preferred regulants are water-soluble mercaptans, ammonium formate and hydroxylammonium sulfate. The regulants are used in amountsof from 0 to 25% by weight, based on the sum of the monomers used in the polymerization. Particularly active regulants, which are preferred, are used in amounts of not more than 15% by weight. If the copolymerization is carried out in the presence of regulants, their minimum use level is 0.2 % by weight, based on the monomers to be polymerized.
Preference is given to polymerizing monomer mixtures of
(a) from 99 to 15 mol % of acrylic acid, methacrylic acid or mixtures thereof,
(b) from 0.5 to 15 mol % of a comonomer of, (b1) maleic anhydride and (b2) ethylene glycol, polyethylene glycol having a molecular weight of up to 2,000, glycerol, polyglycerols having a molecular weight of up to 2,000, pentaerythritol, monosaccharides, neopentyl glycol, .alpha.,.omega.-diamines of from 2 to 6 carbon atoms, .alpha.,.omega.-diols of from 3 to 6 carbon atoms, neopentyl glycol hydroxypivalate or mixtures thereof,
(c) from 0 to 84.5 mol % of maleic acid and/or itaconic acid and
(d) from 0 to 20 mol % of hydroxypropyl acrylates, hydroxypropyl methacrylates, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylates, hydroxybutyl methacrylates or mixtures thereof.
Particular preference is given to the preparation of copolymers of
(a) acrylic acid and/or methacrylic acid,
(b) one of the abovementioned comonomers of formula (I) or (II), and
(c) maleic acid.
The copolymerization of monomers (a) to (e) gives aqueous polymer solutions having a polymer content of up to 70% by weight. It is of course also possible to prepare highly dilute, for example 1% strength, aqueous solutions; however, because of economic considerations the copolymerization is guided in such a way as to prepare not less than 20% strength by weight aqueous copolymer solutions. Following the copolymerization the solutions can be brought to a pH within the range from 6.5 to 7, if the polymerization has not in any case been carried out within this range. The copolymer can be isolated by evaporating the aqueous solution. It has a low residual monomer content and is surprisingly biodegradable. The biodegradability of the copolymer according to the invention as measured under German Standard Specification DIN 38,412, Part 24 (static test (L25)) is up to 100%, generally within the range from 20 to 95%.
The copolymer is water-soluble. If insoluble in water in the free acid form it can be converted into a water-soluble form by partial or complete neutralization with NaOH, KOH, ammonia or amines. A copolymer whose alkali metal or ammonium salts have a solubility in water at 20.degree. C. of not less than 20 g per liter is referred to in the present context as water-soluble. The copolymer surprisingly has the advantage at low concentrations of not precipitating in aqueous solutions which contain Ca and/or Mg ions. For this reason it is possible to prepare a stable solution of the copolymer in tap water without incurring precipitates of an alkaline earth metal salt of the copolymer.
The K value of the copolymer is within the range from 8 to 120, preferably from 12 to 100. The K value of the copolymer is determined at 25.degree. C. and pH 7 on a 1% strength by weight aqueous solution of the sodium salt of the copolymer. If the copolymer is present in the form of another salt or in the form of the free acid, conversion into the sodium salt is necessary before the K value is determined.
The copolymer described above is used according to the invention as a detergent additive. In this use, it can be added to pulverulent or alternatively liquid formulations. Detergent formulations are customarily based on surfactants with or without builders. Pure liquid detergents usually do not include builders. Suitable surfactants are for example anionic surfactants, such as C.sub.8 - to C.sub.12 -alkylbenzenesulfonates, C.sub.12 - to C.sub.16 -alkanesulfonates, C.sub.12 - to C.sub.16 -alkyl sulfates, C.sub.12 - to C.sub.16 -alkyl sulfosuccinates and sulfated ethoxylated C.sub.12 - to C.sub.16 -alkanols, and also nonionic surfactants, such as C.sub.8 - to C.sub.12 -alkylphenol ethoxylates, C.sub.12 -C.sub.20 -al kanol alkoxylates, and also block copolymers of ethylene oxide and propylene oxide. The end groups on the polyalkylene oxides may be capped. This term is to be understood as meaning that the free OH groups on the polyalkylene oxides can be etherified, esterified, acetalated and/or aminated. A further possible modification comprises reacting the free OH groups on the polyalkylene oxides with isocyanates.
The group of nonionic surfactants also includes C.sub.4 - to C.sub.18 -alkyl glucosides and the products obtainable therefrom by alkoxylation, in particular those which are preparable by reacting alkyl glucosides with ethylene oxide. The surfactants usable in detergents can also be of zwitterionic character and be soaps. The surfactant generally accounts for from 2 to 50, preferably from 5 to 45, % by weight of the makeup of the detergent.
Examples of builders present in detergents are phosphates, for example orthophosphate, pyrophosphate and in particular pentasodium triphosphate, zeolites, sodium carbonate, polycarboxylic acid, nitrilotriacetic acid, citric acid, tartaric acid, the salts of the acids mentioned and also monomeric, oligomeric or polymeric phosphonates. The individual substances are used in different amounts in detergent formulations, for example sodium carbonate in amounts of up to 80%, phosphates in amounts of up to 45%, zeolites in amounts of up to 40%, nitrilotriacetic acid and phosphonates in amounts of up to 10% and polycarboxylic acids in amounts of up to 20%, all based on the weight of the substances and on the total detergent formulation. Because of the severe environmental pollution entailed by the use of phosphates, the phosphate content in detergents is being increasingly lowered, so that detergents these days contain not more than 25% of phosphate or preferably are even phosphate-free.
The biodegradable copolymer can also be used as an additive in liquid detergents. Liquid detergents solid surfactants which are soluble or at least dispersible in the detergent formulation. Suitable surfactants for this purpose are those products which are also used in pulverulent detergents and also liquid polyalkylene oxides and polyalkoxylated compounds.
Detergent formulations may also contain as further additives corrosion inhibitors, such as silicates. Suitable silicates are for example sodium silicate, sodium disilicate and sodium metasilicate. Corrosion inhibitors can be present in the detergent formulation in an amount of up to 25% by weight. Further customary additives for detergents are bleaching agents which may be present therein in an amount of up to 30% by weight. Suitable bleaching agents are for example perborates or chlorine-releasing compounds, such as chloroisocyanurates. Another group of additives which may be present in detergents are grayness inhibitors. Known substances of this kind are carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose and graft polymers of vinyl acetate on polyalkylene oxides having a molecular weight of from 1,000 to 15,000. Grayness inhibitors can be present in the detergent formulation in an amount of up to 5%. Further customary additives for detergents are fluorescent whitening agents, enzymes and scents. Pulverulent detergents may also contain up to 50% by weight of an extender, such as sodium sulfate. Detergent formulations can be free of water or contain small amounts thereof, for example up to 10% by weight. Liquid detergents customarily contain up to 80% by weight of water. Customary detergent formulations are described for example in detail in German Laid-Open Application DOS No.3,514,364, which is incorporated by reference.
The biodegradable copolymer described above can be added to all possible detergent formulations. The amounts used for this purpose range from 0.5 to 25, preferably from 1 to 15, % by weight, based on the total formulation. The amounts of biodegradable copolymer used are in most cases preferably from 2 to 10% by weight, based on the detergent mixture. Of particular importance is the use of the additives to be used according to the invention in phosphate-free and low-phosphate detergents. Low-phosphate formulations contain not more than 25% by weight of pentasodium triphosphate or pyrophosphate. By reason of the biodegradability, the copolymer to be used according to the invention is preferably used in phosphate-free formulations.
If desired, the biodegradable copolymer to be used according to the invention may be used together with nonbiodegradable copolymers of acrylic acid and maleic acid or homopolymers of acrylic acid in detergent formulations. The latter nonbiodegradable polymers have hitherto been used as incrustation inhibitors in detergent formulations. Besides the aforementioned polymers it is also possible to use copolymers of C.sub.3 - to C.sub.6 -mono-carboxylic and -dicarboxylic acids or maleic anhydride and C.sub.1 - to C.sub.4 -alkyl vinyl ethers. The molecular weight of the homopolymers and copolymers is from 1,000 to 100,000. If desired, these incrustation inhibitors can be used in an amount of up to 10% by weight, based on the total formulation, in detergents alongside the biodegradable copolymer to be used according to the invention. Although the known incrustation inhibitors based on the abovementioned polymers are not biodegradable, they can nonetheless be removed from the effluent in water treatment plants together with the activated sludge onto which they become adsorbed. The biodegradable copolymer can be added to detergent formulations in the form of the free acid, in completely neutralized form or in partially neutralized form.
The K values given in the Examples were determined by the method of H. Fikentscher, Cellulosechemie 13 (1932), 58-64, 71-74; K=k.10.sup.3. The measurements were carried out in all cases on a 1% strength by weight aqueous solution of the sodium salt of the polymer at 25.degree. C. and pH 7.

EXAMPLES
Preparation of Biodegradable Copolymers
General Method of Preparation
In a glass reactor equipped with a stirrer, a thermometer, nitrogen inlet means and 3 add vessels of which one add vessel is heatable and stirrable, for each Example 98 g (1 mol) of maleic anhydride are dissolved in 500 ml of 4-molar aqueous sodium hydroxide solution, and the solution is heated to 90.degree. C. At the same time, 98 g (1 mol) of maleic anhydride in the heatable add vessel are admixed with 0.1 g of p-toluenesulfonic acid and the polyhydric alcohols specified for each case in Table 1, and the mixture is melted under nitrogen at from 60.degree. to 120.degree. C. in the course of from 0.5 to 3.5 hours.
The copolymerization is carried out at 90.degree. C. in the course of 5 hours by adding the amount of sodium acrylate given in Table 1 in the form of a 35% strength aqueous solution, the melt of the comonomers (from maleic anhydride and polyhydric alcohol and unconverted maleic anhydride) and, over a period of 6 hours, starting with the addition of the monomers and also continuously, 90 g of 30% strength hydrogen peroxide in 100 ml of water. The result obtained is a viscous, aqueous solution which from the end of the initiator addition is polymerized at 90.degree. C. for a further hour. After cooling down, the aqueous solution is brought with 25% strength aqueous sodium hydroxide solution to pH 6.5. The starting materials, the K values, the residual maleic acid content and data concerning the biodegradability of the copolymers are given in Table 1.
Copolymers 11 to 13 were each prepared using polyethylene glycol having a molecular weight of 400.
TABLE 1__________________________________________________________________________ Copolymerization Maleic acid Copolymer Preparation of comonomer (from initial ResidualCopoly- in add vessel by reaction Tempera- Na charge and Como- level of Biodegrad-mer of 1 mol of MA with ture Reaction acrylate the add) nomer K maleic abilityNo. 0.25 mol of [.degree.C.] time [h] [mol %] [mol %] [mol %] value [% by weight] [%]__________________________________________________________________________1 ethylene glycol 60 0.5 63.1 31.6 5.3 35.7 0.18 792 ethylene glycol 60 0.5 63.1 31.6 5.3 27.6 0.23 763 neopentylglycol 60 0.75 84.2 10.5 5.3 62.3 0.19 474 neopentylglycol 60 0.75 63.1 31.6 5.3 27.9 0.22 775 1,4-butanediol 60 0.75 63.1 31.6 5.3 25.6 0.23 796 ethylenediamine was prepared 63.1 31.6 5.3 34.5 0.19 38 separately7 hexamethylenediamine " 63.1 31.6 5.3 38.5 0.17 398 diethylene glycol 100 1.0 63.1 31.6 5.3 22.4 0.15 819 tetraethylene glycol 100 1.0 63.1 31.6 5.3 15.7 0.18 8410 diethylene glycol 100 1.0 63.1 31.6 5.3 17.3 0.17 8111 polyethylene glycol 90 2.0 63.1 31.6 5.3 30.4 0.30 6212 polyethylene glycol 90 2.0 84.2 10.5 5.3 40.2 0.30 7213 polyethylene glycol 90 2.3 63.1 31.6 5.3 28.5 0.34 6914 glycerol 80 3.0 74.8 21.0 4.2 67.8 0.19 4115 glycerol 80 3.0 62.5 33.3 4.2 46.7 0.26 7416 glycerol 80 3.0 62.5 33.3 4.2 36.3 0.34 78Comparison with prior art17 as per EP 25,551: Na salt of copolymer of 70% acrylic acid and 30% maleic acid 60.0 <1018 Na salt of homopolymer of acrylic acid 100.0 <10__________________________________________________________________________ Copolymers 2, 9, 10 and 16 were additionally prepared in the presence of 1% by weight of mercaptoethanol, based on the particular monomers used. MA = maleic anhydride
The copolymers indicated in Table 1 as nos. 2, 9, 11 and 16 were tested in respect of precipitation at pH 7.5 in aqueous solutions containing from 10 to 10,000 mg/l of Ca ions (in the form of CaCl.sub.2). The following Ca ions concentrations were tested: 10, 50, 75, 100, 778 150, 500, 1,000 and 10,000 mg/l. The copolymer concentrations were varied from 0.1 to 7 mg/l (giving the following test concentrations: 0.1, 0.5, 1.0, 2, 3, 4 and 7 mg of copolymer/l of water). In this test, even 20 days of storage of the aqueous solutions of the copolymers in the presence of Ca ions did not give rise to any precipitates, while a copolymer of 30% by weight of maleic acid and 70% by weight of acrylic acid, which had a K value of 60, always gave rise to precipitates under the stated test conditions.
The biodegradability of the copolymers was additionally demonstrated in bacterial growth tests. For this purpose, an enrichment medium was prepared on solid nutrient media and set with 18 g/l of agar. The enrichment medium had the following composition:
______________________________________disodium hydrogenphosphate with 2 H.sub.2 O 7 g/lpotassium dihydrogenphosphate 3 g/lsodium chloride 0.5 g/lammonium chloride 1.0 g/lsolution of trace elements 2.5 ml/l pH 7.0______________________________________ (prepared according to T. Bauchop and S. R. Elsden, J. Gen. Microbiol. 23 (1960), 457-469).
The copolymers described in Table 1 under nos. 1 to 16 were each added to the nutrient media in concentrations of 10 g/l.
Soil samples were either added to the liquid medium and shaken therein at 30.degree. C. for 7 days or applied directly in the form of an aqueous suspension to solid nutrient media and likewise incubated at 30.degree. C. The enrichment cultures in the liquid medium were transferred to solid nutrient media after 7 days. Colonies growing well on these plates were plated out and isolating streaks were examined for purity.
This method led to the isolation of pure bacterial cultures which exhibited clear signs of growth on the copolymers under test.
If, by contrast, the bacterial growth tests described above were carried out for comparison with a copolymer of 30% by weight maleic acid and 7% by weight acrylic acid, which has a K value of 60, no bacterial growth was detectable.
The action of the biodegradable copolymers to be used according to the invention in detergents is illustrated in the Examples which follow. The action of the biodegradable copolymers as builders results from the ability of these polymers to inhibit incrustations on the laundry, to boost the washing power of the detergents and to reduce the graying of white test material on washing in the presence of soil cloth.
To this end, test fabrics are subjected to repeated washes in detergent formulations containing a wide range of builders and either the bio-degradable copolymer to be used according to the invention or for comparison with the prior art a previously used copolymer of acrylic acid and maleic acid. The last three washes of a series were each carried out in the presence of standard soil cloth. The extent to which the whiteness of the test fabric is reduced is a measure of graying. The extent to which the whiteness of the soil cloth is increased is a measure of the washing power of the detergent used and is determined photometrically as percentage reflectance.
Incrustation values are obtained by ashing the polyester/cotton blend fabric or the cotton terry towelling fabric after the test. The ash content is given in weight percent. The lower the ash content of the test fabric, the higher the effectiveness of the polymer present in the detergent. Depending on the effectiveness of the builder used in the detergent, different quantities need to be used of the biodegradable copolymers to be used according to the invention.
______________________________________Test conditions______________________________________instrument Launder-O-Meter from Atlas, Chicagono. of wash cycles 20washing liquor 250 ml, the water used having 4 mmol of hardness per liter (calcium:mag- nesium = 4:1)wash duration 30 min. at 60.degree. C. (including heating- up time)detergent dose 8 g/ltest fabric 5 g of polyester (store no. 655) 5 g of polyester/cotton (store no. 776) 5 g of cotton terry towelling (store no. 295)soil cloth 5 g of WFK 10 D, 10 C and 20 D (standard soil cloth of the Krefeld Laundry Research Institute, Adlerstr. 44) and of EMPA 104 (standard soil cloth of Swiss Materials Testing Institute, St. Gallen (CH)) (cf. Table).______________________________________
This soil cloth was added in each case in wash cycles 18 to 20. Detergent formulations 1 to 29 of Table 2 were prepared and investigated.
The photometric measurement of the reflectance in % was carried out in the present case on an Elrepho 2000 (Datacolor) at a wavelength of 460 nm (barium primary white standard in accordance with German Standard Specification DIN No.5,033).
TABLE 2__________________________________________________________________________Detergent formulations 1 to 9 Composition in parts by weight Detergent component 1 2 3 4 5 6 7 8 9__________________________________________________________________________Surfactants dodecylbenzenesulfonate (50%) 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 C.sub.13 /C.sub.15 -oxoalcohol polyglycol ether (7 EO) 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7 Soap 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8Builders pentasodium triphosphate zeolite A 25 25 25 25 Sodium carbonate 15 12 NTA.sup.(1) 5 5 Na citrate 10 10 Na tartrate phosphate.sup.(2) 2Silicates Na disilicate 6 6 6 6 6 6 6 6 6 Mg silicate 1 1 1 1 1 1 1 1 1Grayness carboxymethylcellulose 1 1 1 1 1 1 1 1 1inhibitorsBleaching agent Na perborate 20 20 20 20 20 20 20 20 20Extender sodium sulfate 47 22 32 42 37 45 10 17 12__________________________________________________________________________Detergent formulations 10 to 17 Composition in parts by weight Detergent component 10 11 12 13 14 15 16 17__________________________________________________________________________Surfactants dodecylbenzenesulfonate (50%) 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 C.sub.13 /C.sub.15 -oxoalcohol polyglycol ether (7 EO) 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7 soap 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8Builders pentasodium triphosphate 10 20 20 zeolite A 25 25 25 25 25 20 sodium carbonate 10 10 10 NTA.sup.(1) 5 Na citrate 10 10 Na tartrate 10 phosphonate.sup.(2) 2 2 1Silicates Na disilicate 6 6 6 6 6 6 6 6 Mg silicate 1 1 1 1 1 1 1 1Grayness carboxymethylcellulose 1 1 1 1 1 1 1 1inhibitorsBleaching agent Na perborate 20 20 20 20 20 20 20 20Extender sodium sulfate 12 20 8 3 11 19 29.5 20.5__________________________________________________________________________ .sup.(1) Trisodium salt of nitrilotriacetic acid .sup.(2) Diethylenetriaminepentamethylenephosphonate
TABLE 3______________________________________Liquid detergent (composition in parts by weight) Detergent component 18 19 20______________________________________Surfactants dodecylbenzenesulfonate (50%) 10 C.sub.13 /C.sub.15 /-oxoalcohol poly- glycol ether (7 EO) 15 15 15 Isotridecanol polyglycol ether (8 EO) 15 15 15Builders Trisodium nitrilotriacetate 6Stabilizer Polypropylene glycol 600 2 2 2Water 63 57 53______________________________________
The detergent formulations indicated in Tables 2 and 3 were tested using the methods described above. For comparison with the prior art the detergent formulations contained either no copolymer or copolymer no. 17 (copolymer as described in EP Patent No. 25,551 of acrylic acid and maleic acid). The detergent formulations used in the Examples and Comparative Examples and the results obtained therewith are indicated in Tables 4 and 5.
TABLE 4__________________________________________________________________________ Addition to detergent % by wt. of ash Washing power Detergent formulation Terry- % reflectance of soilComparative formulation Parts by Cotton towelling clothExample example no. weight Copolymer No. 222 295 WFK 10 C EMPA 104__________________________________________________________________________ 1 1 0 -- 0.50 3.6 55.6 28.41 1 5 1 0.52 2.8 58.8 41.22 1 5 3 0.36 2.9 61.4 41.73 1 5 7 0.34 2.9 55.3 32.0 2 1 5 17 0.42 2.8 59.4 41.4 3 2 0 -- 0.81 2.7 63.9 37.84 2 5 3 0.45 1.2 67.6 47.2 4 2 5 17 0.45 1.2 64.3 48.7 5 3 0 -- 4.6 6.4 55.2 39.55 3 5 7 3.0 5.1 60.2 43.3 6 3 5 17 2.7 4.9 64.2 46.2 7 4 0 -- 0.40 3.7 55.3 30.56 4 5 8 0.33 3.2 57.2 34.9 8 4 5 17 0.33 2.4 6.41 45.0 9 5 0 -- 0.26 1.5 62.2 36.77 5 5 13 0.26 1.0 64.2 50.8 10 5 5 17 0.25 0.99 63.5 46.9 11 6 0 -- 0.42 3.4 56.5 32.48 6 5 12 0.31 2.8 59.2 42.9 12 6 5 17 0.24 1.4 58.2 46.6__________________________________________________________________________ Co/PES 776 WFK 10 D__________________________________________________________________________ 13 7 0 -- 11.0 19.2 67 14 7 5 17 5.64 16.1 679 7 5 2 6.26 16.6 67 15 8 0 -- 2.48 11.1 16 8 5 17 1.36 7.110 8 5 4 1.24 7.5 17 9 0 -- 1.49 8.95 64.5 18 9 5 17 0.55 3.95 67.411 9 5 6 0.82 5.15 68.2 19 10 0 -- 3.10 11.4 64.5 20 10 5 17 1.81 8.82 65.312 10 5 8 1.78 9.75 68.6__________________________________________________________________________ Addition to detergent Detergent formulation % ash Comparative formulation Parts by Cotton Polyester Terry towellingExample example no. weight Copolymer No. 776 295__________________________________________________________________________ 21 11 0 -- 4.0 11.44 22 11 5 17 1.1 6.9013 11 5 2 1.6 6.75 23 12 0 -- 8.5 14.4 24 12 4 17 2.0 10.3 25 12 4 18 3.8 12.514 12 4 13 2.9 11.7 26 13 0 -- 1.2 4.12 27 13 4 17 0.38 1.9415 13 4 14 0.36 1.93 28 14 0 -- 1.11 6.45 29 14 4 17 0.68 3.9016 14 4 15 0.67 3.90 30 15 0 -- 3.52 8.05 31 15 3 17 0.36 0.8617 15 3 5 0.59 1.20 32 16 0 -- 3.75 11.1 33 16 1.5 17 1.5 5.018 16 1.5 11 2.8 6.8 34 17 0 -- 2.35 9.64 35 17 1.5 17 0.20 0.6919 17 1.5 10 0.50 1.84 36 2 0 -- 1.18 4.63 37 2 5 17 0.60 3.0920 2 5 9 0.66 3.88 38 2 0 -- 1.07 1.82 39 2 5 17 0.65 0.6921 2 5 13 0.52 0.67__________________________________________________________________________
TABLE 5__________________________________________________________________________ Addition to detergent Washing power formulation % reflectance of Detergent Pts. by soil clothComparative formulation Copolymer EPMAExample example no. Wt. no. 104 WFK 20 D__________________________________________________________________________ 40 18 0 -- 25.6 56.6 41 18 5 17 27.3 59.822 18 5 1 27.9 60.3 42 19 0 -- 27.2 58.1 43 19 5 17 28.6 61.523 19 5 3 31.8 62.3 44 20 0 -- 23.6 56.3 45 20 5 17 26.6 57.624 20 5 8 25.4 59.2__________________________________________________________________________
Table 5 reveals that the copolymers to be used according to the invention used in Examples 22, 23 and 24 have a better primary washing action compared with copolymer 17 (prior art copolymer) in comparable detergent formulations as per Comparative Examples 40 to 45.

Number	Name	Date
3955920	Krauch et al.	May 1976
4647396	Denzinger et al.	Mar 1987
4686062	Kermode et al.	Aug 1987
4702858	Denzinger et al.	Oct 1987

Number	Date	Country
2333416	Jan 1975	DEX
2910133	Sep 1980	DEX

Detergents containing water-soluble copolymers containing as copolymerized units monomers having two or more ethylenically unsaturated double bonds

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