MXPA97008558A - Soluble copolymers in water, a process for your production and your - Google Patents

Abstract

The present invention relates to water-soluble polymers consisting of a) monoethylenically unsaturated dicarboxylic acids and / or their salts, b) monoethylenically unsaturated monocarboxylic acids and / or their salts, c) monounsaturated monomers which, after hydrolysis or saponification, they can be converted into monomers having a hydroxyl group covalently linked to the CC chain, d) monomers containing acidic sulfonic groups or monoethylenically unsaturated sulfate groups, and optionally e) additional copolymerizable monomers, with the sum of the monomers of a) ae) being 100%. The present invention also relates to a process for the production of these polymers by radical polymerization and hydrolysis in aqueous medium, and with the use of these polymers as additives or coadditives in detergents and cleaners, in the pretreatment of cotton, bleach stabilizers , as auxiliary agents in textile printing, and in the manufacture of leather, as well as for the inhibition of the hardness of water, and as a dispersing agent as well as detergents and cleaner

Description

COPOLLMER08 SOLUBLES BM WATER, A PROCESS FOR ITS PRODUCTION, AND ITS USE The present invention relates to water-soluble copolymers having OH groups covalently attached directly to the polymer chain and based on unsaturated mono- and dicarboxylic acids, vinyl esters or ethers, and monomers containing sulfonic acid / sulfonyl groups. The present invention also relates to a process for its production and its use in detergents and cleaners, in the inhibition of water hardness, as dispersing agents, and in the production, finishing and / or staining of textile and textile fibers, and in leather manufacturing. Because ecological considerations have been put forward in recent years, many of the efforts to develop new polymers have focused on their biodegradability. The products whose application and elimination is carried out in aqueous systems have been of particular interest. In some fields, for example, the paper-making industry has used degradable polymers such as starches, as binders very frequently; In other fields, polymers grafted with renewable raw materials, such as starch or sugar, and synthetic monomers have been developed. However, for many REF: 25971 applications are relatively high technical requirements, and products based on renewable raw materials are not able to meet those standards to the extent that the purely synthetic polymers used to date do so. A typical example is the use of polycarboxylates in mixed sizes for textile fibers; there often a mixture of starch and polycarboxylate is used as a compromise between the degradability and sizing properties. Another important field of application for water-soluble polymers is the use in detergents and cleaners. During the last years, the development of this sector has been determined by the replacement of. the polyphosphate components which, as is generally known, result in overfertilization of waters and, consequently, in problems known as eutrophication. In addition to the main cleaning effect, the polyphosphates have a favorable secondary detergent behavior; they remove alkaline earth metal ions from the aqueous liquor, from textiles and dust, prevent the precipitation of insoluble alkaline earth metal salts on textiles, and keep the powder in the wash liquor in a dispersed condition. In this way the incrustations and redepositions are suppressed even after several washing cycles. Due to their binding capacity by alkaline earth ions and their ability to spread and contain dirt, polycarboxylates, such as polyacrylic acids and acrylic acid / maleic acid copolymers, are currently on the market as substituents of polyphosphates. This latter property is achieved by a particularly easy to use copolymers of acrylic acid / maleic acid [Richter, Winner in Tenside Sürfactants Detergents 24 (1987) 4]. Such polymers are described, for example, in patent applications DE 32 33 776 A1 and EP 76 992 Bl. DE 32 33 776 A1 describes a process for the production of copolymers comprising mono and dicarboxylic units, which is characterized by using a specific peroxide / peroxodisulfate initiator ratio. According to this invention, 10-60% by weight of monomer / dicarboxylic acid anhydride, 90-40% by weight of monocarboxylic acid, and optionally 0-20% by weight of monomers containing no carboxylic groups, which, without However, they are not considered as absolutely necessary, they are used and polymerized in an aqueous medium at 60-150 ° C under partial neutralization.

EP 76 992 Bl describes polymeric organic acids, a process for their production, and their use in detergents and cleaners. 50-95% by weight of unsaturated monocarboxylic acid, 0.5-5% by weight of monomers without acid function, and 0-49% by weight of unsaturated dicarboxylic acid are reacted in a bulk polymerization process, and are used in detergents as additives and scale inhibitors, optionally after of neutralization. The acid-free monomers are selected from the group of vinyl and acrylic ester. The problem of eutrophication has been answered with the use of polycarboxylates. However, these synthetic polymers must be considered as substantially inert towards the degradation process. Due to the existing diffusion and the increasing increase of such polymers, the question arises whether they remain in the ecosystem. Tests in this regard showed that approximately 90% of the polycarboxylates are adsorbed to and disposed of by the sewage sludge, that is, by discharge, agricultural use, or combustion. The biological degradation takes place to a very limited extent, the aforementioned degradation contributes between 1 and 10%. Statements in this regard can be found in the publications of J. Lester et al. The partitioning of polycarboxylic acids in activated sludge ", Chemosphere, Vol. 21, Nos. 4-5, pp. 443-450 (1990), H. Schumann" Elimination von l4C-markierten Polyelektrolyten in biologischen Abwasserreinigungsprozessen, Wasser 'Abwasser (1991) , pp. 376-383, P. Berth "Mdglichkeiten und Grenzen des Ersatzes von Phosphaten in Waschmitteln", Angewandte Chemie (1975), pp. 115-142. The introduction of large amounts of non-degradable compounds into the environment is critical from an ecological point of view. To solve this problem, it seems obvious to use biodegradable polymers, that is, those that can not be emulsified to carbon dioxide and water, or to improve the effectiveness of commercial polycarboxylates in such a way that the concentrations used can be diminished or that they can assume the functions of others. detergent components to help the environment. DE 43 27 494 A1 describes the production of polyaspartic acid imides. Such polycondensates were designed to be used as additives in detergents and cleaning agents. EP 633 310 Al also describes the use of those polymers of limited biodegradability as additives in detergents. In general, however, these polymers have a low binding capacity and dispersion compared to polycarboxylates, that is, they are less effective. Under washing conditions, ie, alkali and elevated temperature, they have the additional disadvantage of destroying the polymer by hydrolysis / saponification under decomposition with simultaneous ammonia. These phosphate substituents represent an ecological problem since the nitrogen attached to the polymer could promote as fertilizer the eutrophication of the waters already known from phosphates. The production of a biodegradable polycarboxylate polymer based on esters of glyoxylic acid is known from US Pat. No. 4,144,256. To achieve technically interesting molecular weights, the aforementioned polymerization method in anhydrous organic solvents requires temperatures of 0 ° C or lower , achieving polymer yields of only 75%, followed by isolation and cleaning steps that reduce performance even more. Since the polymer is unstable in the acidic or alkaline pH range, the final groups thereof must be further blocked chemically. However, the reduced molecular weight caused by the chain cleavage involving loss of activity can occur during the evolution of the carboxyl groups from the ester form by means of saponification. Such polymers are not suitable for use in large quantities because very expensive and commercially unavailable monomers and very expensive polymerization and processing techniques must be employed, in addition to exhibiting the described instability.

Patent GB 1 385 131 describes a detergent composition using a biodegradable maleic acid polymer and vinyl alcohol units. The production process includes a polymerization by precipitation in benzene, the separation and drying of the polymer, and its hydrolysis and saponification in an aqueous alkaline medium. Leaving the relatively complicated and costly production of these polymers out of consideration, the additional disadvantages with respect to the degradability and profile of properties become apparent. According to the indications related to the degradability, there is a drastic decrease in degradation along with the increase in molecular weight. An increase in molecular weight of 4,200 to 18,000 means a reduction in degradation of 63%. With respect to the properties it should be mentioned that an inhibition of redeposition of stains or dirt that is superior to sodium tripolyphosphate can only be achieved in detergent formulations with the content of maleic acid / vinyl alcohol polymer contributing at least 35% . In view of the art, those highly uneconomic polymer concentrations in detergents are disadvantageous; the currently used detergent formulations comprise approximately 5% polymer (DE 40 08 696). According to GB 1 284 815 the maleic acid-vinyl alcohol copolymers are also used as substituents for phosphate in detergents and cleaning agents. It is recommended to use 10-80% by weight, preferably 15-60% by weight, in relation to the detergent or cleaning agent; again, this is also an uneconomically high concentration and, furthermore, points to poor efficiency if lower concentrations are used. EP 0 497 611 A1 discloses the production and use of improved and partially biodegradable polymers based on maleic acid, acrylic acid and vinyl acetate, which are polymerized in an organic solvent and subsequently subjected to aqueous hydrolysis. In addition, the possibility of modifying the polymers by subsequent saponification, optionally followed by an oxidation reaction, is described. Compared to the aqueous process, polymerization in an organic solvent is described as a necessary method since, on the one hand, any desired monomer ratio can be realized in the polymer and, on the other hand, undesirable hydrolysis reactions of the polymer can not occur. the monomers. The degradability of the terpolymers according to EP 0 497 611 Al was tested in a Closed Bottle Test and evaluated on a scale of 0 to 100% BOD (Biological Oxygen Demand) 25 days later. In such a test test, a polyacrylic acid having a degradability of 1.8% and a copolymer of maleic acid and vinyl acetate having an 8% degradability were mentioned. The products manufactured in the organic solvent were examined in hydrolyzed and saponified form with different molar ratios of the monomers used, resulting in a biological degradation of 13.6-28.9%. EP 0 398 724 A2 describes a process for the production of maleic acid / acrylic acid copolymers in aqueous solution, wherein acid-free monomers can also be used. Such a production process is based in particular on the specific simultaneous dosing of all the monomeric components and the other reagents necessary for the polymerization. Although no particular emphasis is given to the biodegradability of the polymers, those values were measured in three comparative examples. Example 1 illustrates the production of a copolymer of maleic acid and acrylic acid indicating biodegradation 30 days later with 3.3% (BOD). Example 5 describes a copolymer of maleic acid, acrylic acid and 10.6% by weight of vinyl acetate having a 9.6% biodegradation (BOD) after 30 days. Example 6 describes a copolymer of maleic acid, acrylic acid and 10.6% by weight of 2-hydroxyethylmethacrylate having a degree of degradation of 7% after 30 days.

US-3 887 480 discloses detergents and cleaning agents produced on the basis of polymers of 35-70 mol% maleic acid, 20-45 mol% vinyl acetate and 2-40 ol acrylic acid. Among other things, the invention was based on the discovery that the reaction of the monomer in aqueous form can be increased by very large amounts of persulfate initiator. The saponification of the polymerized vinyl acetate monomers does not take place, there is no biodegradability. EP 0 193 360 Bl discloses granular detergent compositions having a phosphate content of less than 5% by weight; in addition to using zeolite from 0.1 to 20% by weight, polymers of dicarboxylic acid anhydride, monocarboxylic acid anhydride, and a non-ionic separating monomer of the acrylate ester, vinyl ester or vinyl alcohol type. Furthermore, the production of the terpolymers is not mentioned, and comonomers were not used. The test results with respect to the application technology are not given. US 3 879 288 describes a process for suppressing the hardness of water by adding polymers based on fumaric acid and allyl sulfonate monomer. Due to the low polymerization activity of the monomeric components. the polymer solutions comprise highly intolerable residual monomer proportions; a low binding capacity and dispersion. DE 43 00 772 A1 describes the production of terpolymers having an improved degradability compared to the technique. The aforementioned terpolymers are produced aqueous medium of monomers of the type of the mono-unsaturated dicarboxylic acids, monocarboxylic acids, and monomers which after hydrolysis can be converted into polymeric constitutional units having a hydroxyl group covalently attached to the C-C-polymer chain. The polymers of DE 772 may optionally comprise up to 10 wt% or more of monomers copolymerizable by free radicals. Although the polymers based on the monomers mentioned above according to DE 43 05 396 Al or DE 43 26 129 Al have better properties in the washing and dispersion forms than the commercial maleic acid / acrylic acid copolymers, their complexing properties higher metal ions, for example iron ions (III) in view of commercial complexing agents, such as EDTA, NTA, and alkyl phosphonates, can be further improved to avoid or at least reduce the use of those dubiously ecological substances. Also, the anti-redeposition properties, which were measured by the dispersing action of the soil or grime particles during the washing process, could be improved with respect to an economically and ecologically desirable restriction of the amounts of detergent components. With respect to the processability under alkaline conditions the polymers have a limited stability, ie, that polymer solutions begin to flake under alkaline conditions. The polymers make it possible to prevent hard water precipitations, but also in this case an improved efficiency is required in view of the economy and ecology to reduce polymer concentrations in the feedwater and industrial water. The viscosity of the polymers in a given active substance is lower than that of the commercial detergent polymers based on maleic acid / acrylic acid, however, for reasons of handling and further processing a lower viscosity is desirable. The market requirements are directed to a low viscosity with maximum concentrations of active substance. The terpolymers according to DE 43 00 772 Al can be produced with low residual monomer contents, but with respect to the saturated dicarboxylic acids the maleic acid content is always higher than that of the physiologically acceptable fumaric acid. Water softening formations are known from EP 0 622 449 A2. EP 0 637 627 2 discloses detergent formulations which are free of zeolites and crystalline layered silicates. Both water softeners and detergents comprise polymers which are formed of unsaturated mono and dicarboxylic acids and monomers which generate OH groups by saponification. Additional monomers may optionally be present; however, polymers containing these additional monomers are not used in the application examples nor are there indications of their properties. Consequently, the object was to improve the terpolymers according to DE 43 00 772 Al with respect to their profile of properties. An increase in the ability of "binding of higher metal ions, particularly calcium (II) and iron (III) ions, and in particular at elevated temperatures during washing processes, is desirable for use in auxiliaries, cleaners, treatment agents In addition, an increase in the action of dispersion and suspension of pigments and dust particles is required to improve the effectiveness in the washing processes and, for example in precursors in detergent, the alkaline dispersion and stabilization of the particles of zeolite optionally in aqueous phase As a general improvement which is of particular importance for the incorporation of polymers in liquid detergents or in mixtures designed for spray drying, the polymer solutions should have the lowest possible viscosity with the highest possible dry substance. In addition, the activity as an anti-deposition agent or crystallization inhibitor is increased so that the The active amount can be reduced, for example, when all polymers are used for process water in heat exchangers, steam generators or in the concentration of sugar syrups. When polymers are used in the manufacture of leather it is important that they fix the chromium and of 'breadth, softness, grain strength and color. Biodegradability should be preserved when the polymers are modified. With respect to the residual monomer content a further reduction must be achieved, and the maleic acid portion in the unsaturated dicarboxylic acid mixture should be made at the same time. More surprisingly, this object has been achieved by the production and use of copolymers obtainable by mixtures of monomers polymerizable by free radicals of a) 10-70% by weight of monoethylenically unsaturated C4-T-dicarboxylic acids or their salts b) - 85% by weight of C3-? Mono- or monoethylenically unsaturated monocarboxylic acids or their salts c) 1-50% by weight of monounsaturated monomers which, after hydrolysis or saponification, release hydroxyl groups attached to the polymer chain d) 0.1-40% by weight of monoethylenically unsaturated monomers comprising sulfonic acid groups and / or groups sulfate e) 0-10% by weight of monomers copolymerizable by additional radicals, with the sum of the monomers according to a) to e) accounting at 100%, in aqueous solution and subsequent saponification of the monomeric components according to ac). Suitable monomers of group a) include dicarboxylic acids of C4-C? monoethylenically unsaturated, their anhydrides or their alkali and / or ammonium salts and / or amine salts. Suitable dicarboxylic acids, for example, are maleic acid, fumaric acid, itaconic acid, methylene malonic acid. It is preferred to use maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, as well as the corresponding sodium, potassium or ammonium salts of maleic or itaconic acid. The monomers of group a) are present in the monomer mixture in the degree of 10 -70% by weight, preferably 20-60% by weight, and more preferably 25-55% by weight. Suitable monomers of group b) include C3 to Cι monoethylenically unsaturated carboxylic acids and their alkali and / or ammonium salts and / or amine salts. These monomers include, for example, acrylic acid, methacrylic acid, dimethyl acrylic acid, ethyl acrylic acid, vinyl acetic acid, allylic acetic acid. Preferred monomers of this group are acrylic acid, methacrylic acid, mixtures thereof, as well as sodium, potassium or ammonium salts or mixtures thereof. The monomers of the group are present in the monomer mixture in a degree of 20 -85% by weight, preferably 25-60% by weight, and more preferably 30-60% by weight. The monomers of group c) include those which - after polymerization - release one or more hydroxyl groups, which are covalently attached directly to the CC-polymer chain, in a cleavage or separation reaction, for example by acid hydrolysis or alkaline saponification of the polymer. Examples thereof are: vinyl acetate, vinyl propionate, acetic acid-methyl vinyl ester, methyl vinyl ether, ethylene glycol monovinyl ether, vinylidene carbonate. The monomers of group c) are present in the monomer mixture to a degree of 1-50% by weight, preferably 1-30% by weight, more preferably 1-20% by weight, and more preferably 1-20% by weight. - 15% by weight. Suitable monomers of groups d) include, for example, sulphonic groups and monomers containing sulfate groups, such as (allyl sulfonic acid), vinyl sulfonic acid, styrene sulfonic acid, acrylamidomethylpropane sulfonic acid, as well as hydroxyethyl sulfates (methyl) ) acrylate, (meth) allyl alcohol sulfates as well as their alkali and / or ammonium salts. Particularly preferred are (meth) allyl sulfonic acid and sulfates of (meth) allyl alcohol. The monomers of group d) are present in the monomer mixture in a degree of 0.1 - 40% by weight, preferably 0.5 - 25% by weight, more preferably 1-10% by weight, and more preferably 1 - 10% by weight. -5% by weight. The monomers of group e) are used simply and optionally to modify the polymers. The monomers of group e), which may optionally be used in the copolymerization, include, for example, non-conjugated, doubly ethylenically unsaturated compounds which normally act as crosslinking agents and increase the molecular weight of the polymers; those should be used in limited quantities. In addition, the polymers can be modified by those monomers of groups e) which change the solubility behavior or cause a character partially similar to that of the surfactants or hydrophobic, such as N-alkyl acrylamides, esters of C-alcohols. 18 alkoxylates, or polyalkylene glycol ester of (meth) acrylic acid, and polyalkylene glycol ester of (meth) allyl alcohol, which may optionally be end capped. The monomers of group e) are optionally present in the monomer mixture up to 10% by weight. The copolymers are manufactured in aqueous solution at 40-180 ° C in the presence of polymerization initiators that form radicals under the polymerization conditions, for example, inorganic and organic peroxides, persulfates, azo compounds and so-called redox catalysts. Suitable polymerization initiators include, for example, acetylcyclohexane sulfonylperoxide, diacetylperoxydicarbonate, dicyclohexylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl perneodecanoate, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). , 2,2'-azobis (2-methyl-N-phenylpropione-midin) dihydrochloride, 2,2'-azobis- (2-methylpropionamidine) dihydrochloride, tert-butyl perpivalate, dioctanoyl peroxide, dilauroyl peroxide, 2, 2'-azobis- (2,4-dimethylvaleronitrile), dibenzoyl peroxide, tert-butylper-2-ethylhexanoate, tert-butylpermaleinate, 2,2'-azobis- (isobutyronitrile), dimethyl isobutyrate 2, 2'-azobis, sodium persulfate, potassium persulfate, ammonium persulfate, bis- (tert-butyl peroxide) -cciohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl peracetate, hydrogen peroxide, 2,2 '-bis- (tert-butyl peroxy) -butane, dicumyl peroxide, di-tert-butyl peroxide, peroxide of di-tert-amyl, piperane hydroperoxide, p-methane hydroperoxide, cumol hydroperoxide, and tert-butyl hydroperoxide. The initiators are adapted to the polymerization temperature chosen according to their half-life can be used alone or in mixture with others. 0.01 to 20, preferably 0.05 to 10% by weight of the polymerization initiator or of a mixture of several polymerization initiators, is used in relation to the monomers used in the polymerization. As a matter of fact, redox coinitiators can also be used in the copolymerization, for example, benzoin, dimethylaniline, ascorbic acid, as well as organically soluble complexes of heavy metals, such as copper, cobalt, iron, manganese, nickel and chromium. Reducer of the redox catalyst can be formed, for example, by compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfocylate and hydrazine.Using the redox coinitiators it is possible to carry out the polymerization at a lower temperature. of normally used redox conisers account for approximately 0.01 to 5% in the case of reducing compounds, and 0.1 to 100 ppm, preferably 0.5-10 ppm in the case of heavy metals, if the polymerization of the monomer mixture starts in the upper limit of the temperature range suitable for the polymerization and then ends at a higher temperature, is advisable use at least two different initiators that decompose at different temperatures, so that a sufficient concentration of radicals is available at each temperature interval. Since the exclusive use of persulfate usually results in broad molecular weight distributions and a low residual monomer content, and the exclusive use of peroxide results in narrower molecular weight distributions and a high residual monomer content, it is sometimes It is advantageous to use a combination of peroxide and / or persulfate, reducing agent and heavy metal as the redox catalyst. The copolymerization can also be carried out by the action of ultraviolet radiation and the presence of photoinitiators or photosensitizers. For example, those are compounds such as benzoin and benzoin ester, α-methylbezoin, or α-phenylbenzoin. Also, so-called triplet photosensitizers such as benzyl-ketals can be used. If the molecular weight should be controlled, polymerization regulators are used. Suitable regulators include mercapto compounds, aldehydes, heavy metal salts. If the polymerization is carried out in the presence of regulators, they are used in amounts ranging from 0.005 to 20% by weight, relative to the monomers. The molecular weight can also be controlled by choosing the material of the polymerization reactor; for example, the use of steel as the reactor material results in lower molecular weights than the use of glass or enamel. In addition, the molecular weight can also be controlled by the amount of initiator. For example, increasing the peroxide content in a peroxide / persulfate initiator mixture can decrease the average molecular weight of the polymer. Particularly preferred is an alternative process wherein a further addition of peroxide, in particular hydrogen peroxide, is effected, after the end of the dosing of the initiator, with the proviso that the molecular weights of the polymers according to the invention decrease.

The polymerization is carried out in conventional polymerization vessels at temperatures of 40-180 ° C, optionally under pressure if the boiling temperatures of the reactants are exceeded.A preferred polymerization temperature ranges from about 60-120 ° C. performed in an inert gas atmosphere, if necessary created by nitrogen injection, excluding atmospheric oxygen.The monomeric components are prepared either as a whole in aqueous solution, or are polysteized by adding the initiator system. a preferred embodiment is introduced into the polymerization reactor for a period of 1-10 hours, preferably 2-8 hours.According to one embodiment of the present invention, the monomer a) and the monomers b) are prepared ) are introduced into it, either in a mixture or separately, According to a preferred embodiment, the monomers a) and d) are prepared together, and the monomers tantes are dosed to these later. The initiator system is added in parallel with the monomers, after the termination of the monomer dosage the addition thereof preferably continues while the monomeric reaction is complete. It has been proven not to be advantageous for the course of the initial polymerization to prepare a small portion of the initiator or initiator mixture. For the purpose of obtaining copolymers having a low residual maleic acid tablet to suppress a premature saponification of the monomers of group c), the acidic monomers employed are neutralized, at least partially. This can be effected by neutralizing or partially neutralizing the monomers prepared according to a) and optionally b), or by complete or partial neutralization of the monomers according to b) and optionally e), which must be dosed. However, in this connection, it is necessary to avoid neutralizing or partially neutralizing the monomers containing carboxylic acid during the polymerization by dosing the lye in the reactor with the simultaneous dosing of the vinyl esters; otherwise, premature saponification of the monomers could result in the formation of acetaldehyde and brown reaction product. As an alternative it is possible to prepare the monomers according to a) and optionally d) in a mainly neutralized form, and introduce the monomers to be dosed substantially in their acid form. The first object of these measures is to avoid premature hydrolysis of the monomers according to c), and the second is to maintain a reasonable polymerization rate. With regard to the use of monomers according to ac) phase separation can take place due to differences in miscibility at certain mixing ratios with water or in mixtures with the other partially neutralized monomers, in particular when large portions of monomers are present c ). This can result in problems of the monomer dosing course and polymerization, or in undesirable hydrolysis of the monomers c). Such problems can be avoided by using surfactant compounds; these are mainly used in the form of anionic and nonionic detergents or their mixtures. Polymerization in the presence of surfactants simultaneously reduces the residual monomer content and improves the dispersive properties of the polymers. Anionic detergents include sodium alkyl benzene sulfonates, alkyl sulfonates, and fatty alcohol sulfates and fatty alcohol polyglycol sulphates. In particular, the following are mentioned: C ben-C? 2 alkyl benzene sulfonates, C? 2-C16 alqu alkyl sulfonates, such as sodium dodecane sulfonate, C12--C16 alquilo alkyl sulfates, such as Na lauryl sulphate, C 2 2-6 alkyl sulfosuccinates, ethoxylated C 2 - 6 alkanoles, sulfates. Additionally, sulfated alkanolamine soaps, α-ester sulfonates, fatty acid monoglycerides or the products of the reaction of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are suitable. further, the products of the carboxymethylated reaction of 3 to 20 moles of ethylene oxide with C? 2-? 6 fatty alcohols or C? -? 2 mono- or dialkylphenols as well as partial fatty alcohol phosphorus esters of C? 2_ ? 6 Ethoxylates are also suitable. Suitable for use as nonionic, low molecular weight surfactants are mainly the water-soluble addition products of 3 to 40 moles of ethylene oxide to 1 mole of fatty acid, alkylphenol, fatty acid, fatty acid amide, alean sulfonamide, or sorbitan fatty acid ester with HLB values of 8 to 18. Particularly suitable are the addition products of 5 to 16 moles of ethylene to coconut or bait fatty alcohols, to oleyl alcohol, to synthetic alcohols with 8 to 16 atoms of carbon, as well as mono- or dialkylphenols having from 6 to 14 carbon atoms in the alkyl groups. The ethoxylation products can optionally also comprise up to 90% by weight of propylene oxide, based on the total alkylene oxide content. The addition products, which comprise ethylene and propylene oxides incorporated by condensation, can be optionally modified by butylene oxides in amounts of up to * to 50% by weight, in relation to the total alkylene oxide content, the butylene oxide is incorporated by condensation.

Suitable non-ionic detergents also include the alkyl polyglycosides modified with C 4 - 8 alkyl groups and having a degree of oligomerization of 1 to 10 glucose units, and water soluble alkoxylation products obtainable by the reaction of those alkyl polyglucosides with ethylene oxide. The polymeric, nonionic surfactant compounds include water soluble cellulose or starch derivatives obtainable by methylation, alkoxylation with ethylene or propylene oxide, and by carboxymethylation, such as methylcellulose, hydroxyethyl- or hydroxypropyl cellulose, or carboxymethylcellulose. Additionally suitable are partially saponified polyvinyl acetates having a degree of saponification of 50-95% and grafted polymers of vinyl acetate on polyethylene glycol. The surfactant compounds are added mainly in amounts of 0.1 to 5% by weight, in particular 0.5 to 2% by weight, based on the sum of the monomers. During the polymerization they are added to the prepared monomers, or mixed with the other components, or dosed in the reactor separately. Copolymers manufactured using maleic acid usually have a residual monomer content that substantially consists of free maleic acid, in addition to small amounts of fumaric acid. For example, Comparative Example 2 relates to a polymer according to DE 43 00 772 which gives a residual maleic acid content of 2530 ppm and for fumaric acid of 300 ppm. More surprisingly, using (meth) allyl sulfonate in the monomer mixtures according to the invention results in polymers whose ratio of maleic acid to fumaric acid is clearly in favor of fumaric acid. This is extremely advantageous since maleic acid could be avoided from the ecotoxicological point of view. For example, the LD 50 (rat, oral) values of maleic acid are 708 mg / kg and those of fumaric acid are 10,700 mg / kg. As soon as the polymerization is complete, the low-boiling components, for example the residual monomers, or their hydrolysis products are distilled if necessary, optionally under vacuum. It is often advantageous to carry out this distillation step, during the polymerization, for example, to remove the low-boiling components or to damage the polymerization. The reconcentration of the aqueous polymer solutions can also be carried out with the distillation. The polymer solutions concentrated in this manner have a lower viscosity than polymerized polymers with a higher concentration than the starting one. The low viscosity polymers have a higher concentration and can also be obtained by substituting a portion of the aqueous phase in the polymerization batch to dissolve the monomer batch by a determined polymer solution. The hydrolysis or saponification of the monomers according to ac) is carried out in an acidic or basic medium, pH values of at least 6.5 as well as 10 are preferred. Depending on the type of monomer, the saponification is carried out at 60.degree. 130 ° C. The duration of the saponification depends on the chosen pH values and the temperature, which fluctuates between 0.1 and 8 hours. The pH values required in the polymer solution to be saponified for the purpose of saponification can be adjusted by adding solid, liquid, dissolved or gaseous inorganic or organic acids or bases. Examples thereof include: sulfuric acid, hydrochloric acid, sulfur dioxide, toluene-p-sulfonic acid, sodium hydroxide solution and potassium hydroxide solution. The readily volatile reaction products formed during saponification can be removed by distillation, optionally under vacuum. A preferred embodiment is the alkaline saponification carried out without prior distillation of the residual monomers and the hydrolysis products in the presence of peroxides, and the remaining residual monomers and the products of the hydrolysis are polymerized in situ or oxidized with less carboxylic acids. dangerous. The degree of saponification of the saponifiable monomer units is 1-100%, preferably 30-100%, and more preferably 60-100%. At the end, the aqueous polymer can be fixed at the pH value required for the respective application.

At this point, known agents are used, such as bleaches and bases, mineral acids, carboxylic acids and polycarboxylic acids. Examples thereof include mineral acids and acid anhydrides, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfur dioxide, and sulfur trioxide; organic acids can be used formic acid, acetic acid, citric acid, tartaric acid, toluene-p-sulfonic acid. Examples of solutions include sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide or ammonium, amines, alkanolamines, and hydroxylamines. In principle, the polymerization can also be carried out as a suspension polymerization; the aqueous monomer phase is dispersed using stabilizers of the suspension in an organic phase, for example consisting of cyclohexane, and then polymerized and saponified in the form of this suspension. Subsequently, the water in the suspension can be removed by azeotropic distillation, and the solid polymer particles can be easily filtered out of the organic phase and used after being dried. Another possibility of manufacturing pulverized polymers is to spray-dry the polymer solution according to the present invention. For example, washed powders can be obtained by spray drying directly from a common solution or suspension consisting of the polymer solutions according to the present invention and the additional detergent components. More surprisingly, it has been found that the polymer solutions according to the present invention have an improved alkali resistance and the monomer content d) in the monomer mixture is less than 10% by weight, and more preferably lower to 7% by weight. If the polymer solutions are fixed at alkaline pH values, as is usual for example in the production of detergents, there are no changes, whereas the polymers according to DE 43 00 772 A1 start to scale later or at the same time. The particular improved alkali resistance shows advantages when the polymers become alkaline some time before being further processed. The polymers described above increase in the molecular weight range from 500 to 5,000,000, the low molecular weight products having molecular weights below 70,000 are absolutely suitable for use as coadditives. It has become evident in the application of technological examinations that the polymers according to the present invention in the molecular weight range of 20,000 and less, develop an excellent action in detergents and cleaners, and have good dispersion and suspension capacity of powders. In addition, they are almost completely removed in the sewage sludge elimination test (OECD standard 303 A). Biodegradability was determined by the standard according to the OECD 302 B guidelines where the amount of C02 resulting from the degradation was measured and according to the standardized composition test according to ASTM D 5338/92 also measuring biodegradation based on the generation of C02. The polymers meet the requirements for their use in detergent because they can be easily eliminated and degraded. It has surprisingly been found that monomers according to ad) *, in particular methallylsulfonic acid, can control molecular weight, so that the polymers according to the present invention, in addition to their excellent effectiveness, can also be produced with a low viscosity at a high active content. The polymers according to the present invention have a viscosity of about 500 mPas at 40% active contents, while the polymers according to DE 43 00 772 have a viscosity of about 1,100 mPas with a comparable active content. A commercial copolymer based on maleic acid and acrylic acid and used in detergents has a viscosity of approximately 3600 mPas, the asset content is also 40%. The low viscosities of the polymers according to the present invention are generally advantageous when used, and in particular when incorporated, as a component in laundry detergent formulations. For this reason, the polymers of the present invention are excellently suited for detergent and cleaner formulations which are completely or partially manufactured by spray drying, or which are to be used in compaction processes with the lowest possible water content. It is possible to manufacture easy-to-handle suspensions by an undisturbed spray process, and on the other hand it becomes possible to handle a simplified production such as, for example, compact detergent granules by means of extrusion, where the active substance is to be incorporated in the mixture with the lowest possible amount of water to form dry granules, which flow freely or to minimize the possible drying expense. If the polymers to be used in liquid detergents can be modified with hydrophobic comonomers, for example, the monomers of group e). The dissolution behavior of the polymers in the liquid phase of the liquid detergents can be adapted by virtue of this. Consequently, the subject matter of the present invention also relates to detergents and cleaners, in particular detergents for textiles, which comprise the polymers according to the present invention. Preferably, the polymers are used in amounts of 0.5-30% by weight, particularly 2-25% by weight. It is further preferred that, in addition to the polymers, the agents comprise one or more ingredients from the group of inorganic alkaline salts and additive substances normally used in detergents and cleaning agents. The agents according to the present invention can be in solid, granular or liquid form for paste and can be produced with known production methods such as the processes of spray drying, mixing, granulation and / or extrusion. In this regard it is also possible to use a combination of additives in the form of a compound as a components mixed with other granular components of laundry detergents and cleaners. Such combinations of additives, which also form part of the present invention, comprise the polymers according to the present invention and-according to a preferred embodiment-1-30% by weight of the polymers according to the present invention and 50- 70% by weight of zeolite and / or crystalline layered silicates. Combinations of additives comprising 5-30% by weight of sodium carbonate, 0-10% by weight amorphous silicates, 0-25% by weight, salts of organic polycarboxylic acid, and 0-5% by weight are also preferred. weight of conventional (co) polymeric acrylates. Due to the excellent dispersion / suspension properties of the polymers according to the present invention, the aqueous suspensions of the above composition have excellent stability to sedimentation. In addition, the additive combinations can additionally comprise liquid or waxy components, preferably surfactants. Alkaline inorganic salts include water soluble bicarbonates, amorphous silicates, or mixtures thereof, in particular alkali metal carbonate and alkali metal silicate are used. The alkali carbonate content of the agents can be from 0 to about 20% by weight, the alkali metal silicate content of the agents in general can be from 0 to about 10% by weight. It is preferred to use sodium silicate and sodium carbonate. The known additives commonly used in laundry detergents and cleaners are mainly phosphates, zeolites and layered silicates; the zeolite and the crystalline layered silicates are preferred. Suitable zeolites have an average particle size of less than 10 um and preferably comprise 18-22% by weight of bound water. The crystallized, layered silicates represent a substitute or partial substitute for the phosphates and zeolites; in particular the disilicates of ß- and d-sodium Na2Si205 and H20. Agents according to the present invention preferably comprise zeolite containing water and / or crystalline layered silicates in amounts ranging from 10 to 65% by weight. Suitable suitable organic additives include, for example, polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, polyaspartic acids, nitrilotriacetic acid, and mixtures thereof. They are preferably used in the form of salts, their content in the agents preferably being 0-20% by weight. In addition to the polymers of the present invention detergents and cleaning agents may also comprise the known and customary homo- and copolymer polycarboxylates based on (meth) acrylic acid and / or maleic acid, and optionally additional monomers and grafted components, as well as polyacetals which originate from the reaction of dialdehydes with polycarboxylic acids. The portion of those polycarboxylates in the laundry detergents according to the present invention should not exceed 2% by weight. In the production of detergents for dyed textiles, so-called decolorization inhibitors can be added. These substances prevent the transmission of dyes from textiles or parts of textiles heavily dyed to textiles or parts of undyed or slightly colored textiles. The same applies to prevent the transmission of optical brightening agents. It is preferred that 0.1-5% by weight of the polymers or copolymers of vinylpyrrolidone, vinyl oxazolidone, vinyl imidazole, polyamine-N-oxides, optionally supported by cellulase, are used as decolorization inhibitors. The laundry detergents and cleaners of the present invention comprise additional customary ingredients in particular 10-40% by weight of anionic, nonionic, amphoteric, zwitterionic, and / or cationic surfactants. Suitable anionic detergents include those of the sulphonate and sulfate type, for example, alkyl benzene sulfonates, olefin sulphonates, alk (en) yl sulfates, sulfonsuccinic acid esters, ethoxylated fatty alcohol sulfates, α-sulfo fatty acids or their esters, and sulfated fatty acid glycerol esters or mixtures thereof. Anionic detergents can also be used in the form of fatty acid soaps. The ethoxylated C 9 -C 8 alcohols, alkyl glucosides and alkyl esters of alkoxylated fatty acid are preferably used as nonionic detergents; additional surfactants of the amine oxide type, alkanolamine soaps, and polyhydroxy fatty acid amines. The use of nonionic cellulose ethers of the methylhydroxypropyl cellulose group having a portion of 15-35% by weight of methoxy groups and 1-15% by weight of hydroxypropyl groups has proven to be successful in the removal of spots containing grease and oil on textiles. Laundry detergents and cleaners according to the present invention may additionally comprise 15-45% by weight of additional conventional ingredients, such as antiredeposition agents (stain removers), foam inhibitors, bleach and bleach activators, optical brighteners, enzymes, fabric softeners, dyes and aromatic principles, as well as neutral salts. Foam inhibitors are generally used in amounts of 0-8% by weight. Normally soaps, silicone oils or hydrophobic silica acids are used. In the case of defoamers which are not surfactants, amounts in the range of 0-3.5% by weight are generally sufficient due to the stronger effect compared to soaps. The optical brighteners, also called bleaching agents (fluorescent), absorb the UV portion in the wavelength range of about 350 nm, which is invisible to human eyes, and emit blue fluorescence of about 440 nm (500 nm). The fluorescent radiation, for example, of the whitening agents absorbed on the textile fibers during washing, adds to the visible light reflected; in this way the probable yellow hue of a white cloth, which sometimes occurs after several uses and cleanings, not only regenerates to white again, but also achieves a total intensified white color. The stilbene derivatives are particularly suitable not only for use as brighteners; but also structures of coumarin- and quinolon- (carbostyryl) - and 1,3-diphenylpyrazoline, naphthalene dicarboxylic acid and cinnamic acid derivatives can be used, as well as combinations of benzoxazole and benzimidazole structures with conjugated systems. The optical brighteners are used in the range of 0 to 5% by weight, preferably in the range of 0.1 to 0.3% by weight. Enzymes are almost indispensable ingredients in laundry detergents for all purposes and in many other formulations for washing and cleaning. For example, pancreatin (trypsin), proteases, amylases, cellulases, and lipases are used. Its application range is between 0 and 3% by weight, preferably 0.3 and 1.3% by weight. Laundry Detergents (Wl to W10) with the following composition were manufactured with the polymers according to the following invention, the quantity indications relate to the weight percent: Basic materials 1 W2 W3 W 5 6 7 8 9 10 Alkyl of C9-u 9 2 6 6 5 ~ benzenesulfonate of Na sulphate of alcohol 4 7 2 2 7.5 fatty of bait of Cis-iß Sulfate of alcohol 2 fatty of C12-13 of Na C12-13 fatty alcohol 5 4.3 18 15 14 4.5 4.5 2.5 EO Fatty alcohol of Ciz-u 5 7 with 7 EO Fatty alcohol of Ciß-ia 2 with 14 EO Fatty alcohol of bait 1.8 2.5 2 2 2 2 with 5 EO Glycerol with 19 EO 3 Fatty acid soap of 0.8 4 3 4 1 1 5 5 2 tppoliphosphate 10 5 zeolite NaA 23.5 30 25 5 38 35 silicate layered 35 8 crystalline bentonite 5 sodium silicate 3 3 7 3 3 3 5.5 amorphous citrate 8 16 sodium carbonate 12.6 8 11 5 5 3 25 30 9 sodium bicarbonate 25 perborate -monohydrate 16 5 16 16 perborate-tetrahydrate 25 15 tetraacetylenediamine 5.5 5.5 5.5 2 cerboximethyl cellulose 0.25 1.5 polyvinyl pyrrolidone 0.8 granulated enzyme 1 0.6 1 1 1 0.45 granulated antifoam 0.2 0.2 0.2 0.2 optical brightener 0.2 0.2 0.2 0.2 water, salts, perfume rest rest rest rest rest rest rest rest rest polymer according to 5.5 4 3 3.5 5 5 2 20 15 3 the invention of Example 2 The formulations according to the present invention can be used as laundry detergents for textiles in domestic and industrial cleaning processes. The polymers according to the present invention contained in the formulations have an excellent binding capacity for multivalent metal ions and a highly dispersive powder. For this reason, the use of water softeners, such as zeolite or crystalline sodium layered silicates, can be dispersed to some degree. Laundry detergents according to the present invention result in dust removal and stain dispersion and cause only slight fouling during washing of textiles with hard water. Laundry detergents can be strongly foaming formulations, such as those used in handwashing, or they can be surfactant systems that regulate the foam used in laundering laundry. Another subject matter of the present invention relates to hard surface cleaners, and in particular, phosphate-free cleaning agents for dishwashing machines, wherein the polymers according to the present invention are advantageously used due to their complexation and dispersion properties. Detergents for typical dishwashing machines have a high alkalinity and substantially consist of ingredients of the alkaline triphosphate type (15-30% by weight), alkaline metasilicate (20-60% by weight), liquid sodium silicate (0- 5% by weight), alkaline carbonate (5-30% by weight), non-foaming surfactants (0.5-2% by weight), bleaches (4-7% by weight), and chlorine separators (0-5% by weight ). The innovative ecological cleaners are free of phosphate and of low alkalinity and are based on citrates, polycarboxylates, and carbonates intended to be dispensed with substances that eliminate chlorine. The formulations according to the present invention for detergents for dishwashing machines comprise 1-60% by weight, of the polymers according to the present invention, 5-90% by weight of alkali formers, 0-60% by weight of dispersing and complexing agents, 0-10% by weight of low foam surfactants, and 0-50% by weight of additional additives. Additional alkali formers primarily include water-soluble alkali silicates, such as alkali etasilicates, alkali disilicates, and crystalline alkali-layered silicates. In addition, the alkali-reacting salts, such as the alkali hydroxides, alkali carbonates, and alkaline acid carbonates also belong to the group of alkali formers. The amount of these alkaline substances is preferably between 5 and 70% by weight, more preferably between 5 and 55% by weight. The formulations may also comprise dispersing and complexing agents. Suitable products include citrates, phosphonates, homo and copolymers of acrylic acid, isoserin diacetic acid, ethylene diamin tetraacetic acid and nitrilotriacetic acid, as well as the alkali salts of the aforementioned compounds. If these compounds are used in the formulations, their amount is preferably between 5 and 50% by weight; Sodium citrate in sodium citrate concentrations of 10-40% by weight are particularly preferred. In addition, the formulations may also contain low foaming surfactants, preferably in amounts of 0.5-5% by weight. Particular preference is given to non-ionic, low-foaming detergents, for example, ethylene oxide, (1-20 moles) - propylene oxide (1-20 moles), addition products for 1 mole of aliphatic alcohols, carboxylic acids , fatty amines, carboxylic acid amides, and alkanesulfonamides having 10-20 carbon atoms, or compounds of the above substances which are end-capped with alkyl groups. In addition, C8-22 alkyl polyglycosides and polyglycol ethers are used only partially soluble in water, or are combined with nonionic detergents. A maximum surfactant content of 2% by weight is particularly preferred. The formulations may also comprise additional additives. Such additives are oxygen-based bleaching agents, for example, perborates and percarbonates, and persalts of organic acids, such as perbenzoates; they comprise amounts of 0.5-20% by weight, preferably 5-15% by weight; 'Bleaching agents that separate chlorine are used in amounts of 0-5% by weight, if not all. The addition of stabilizing additives to the bleach, for example magnesium salts and / or borates, is advantageous. Oxygen bleach is provided either using suitable bleach activators, or is ready in principle at low wash temperatures. At this point, tetraacetylated diamines, for example TAED (tetraacetylethylenediamine), are preferably used, in amounts of 0-10% by weight, maximum amounts of 5% by weight are particularly preferred. To improve the removal of protein and food particles containing starch, the formulations may comprise enzymes of the type of proteases, amylases, lipases and cellulases. The amounts added advantageously are in the range of between 0.1 and 5% by weight, a maximum amount of 2% by weight is preferred. Fragrances and dyes, defoaming agents, free-flowing agents, silver protectants, adulterants and adjuvants can be easily added to the dishwashing agents according to the present invention as additional ingredients. The formulations for washing dishes according to the present invention can be liquid products, of the pulverized type and granules or products compressed in blocks or tablets.

Liquid formulations can be produced by mixing the components. The pulverized products are mostly manufactured by mixing the pulverized components and optionally spraying the liquid components, or by spray-drying a liquid batch similar to a paste of the starting components. The production of pellets is carried out by mixing the raw materials first and / or by a preliminary treatment in mist blowers, and then they are compressed in machines for making pellets. According to the present invention contained in the formulations have an excellent binding capacity for multivalent metal ions and a very good dispersibility and to carry stains or dirt. For this reason they have an advantageous effect in the formulations for washing dishes according to the present invention, that is to say they support the removal of dust and dispersion of the stains or dirt and reduce the depositions of hard water elements on the products to be cleaned. and about the parts of the machine. The cleaners for use in dish washing machines (C1-C8) were produced with the polymers according to the present invention, they have the following composition (indications in% by weight): Basic materials Cl C2 C3 C4 C5 C6 C7 cß Fatty alcohol of 2 2 2"~" "Fatty alcohol of 0.9 0.9 2 1 C12-18 with 1E02P0 Fat alcohol 2 of coconut of C12-14 with 1P0-3E0 ether octyl -1,2P0, 2 6E0 butyl polymer of 10 8 10 10 5 8 5 15 according to inv. of Ej. 2 dihydrate of 35 30 40 30 35 15 sodium citrate pentahydrate 50 50 sodium metasilicate sodium disilicate 20 10 sodium sodium hydroxide 10 sodium carbonate 28 20 5 13 6 40 5 10 carbonate acid of 35.5 30.1 38 10 sodium monohydrate of 10 5 7 10 3 sodium perborate sodium perborate 12 tetraacetylethylene- 3 2 3 2 ~ * 4 1 diamine enzyme (amylase / protease = 1: 1) sodium sulfate 33 perfumed oil 0.6 0.6 0.4 manganese sulfate (III) add water until 100% by weight The polymers according to the present invention can also be advantageously used as auxiliary agents in the finishing of textiles or textile materials. For example, in the boiling or whitening of the cotton autoclave, here they join the hard constituents and disperse the substances or impurities that accompany the cotton so that its redeposition is prevented, and they support the action of the surfactants. The polymers according to the present invention are used as stabilizers in peroxide bleaching; when additional stabilizing silicates are used, they prevent silicate deposits. The polymers according to the present invention can also be used as auxiliary agents in continuous and discontinuous washing and batch liquors; here the unfixed dye is removed and the product is washed more, quickly, and the carving is achieved. In the case of polyester fibers, the dispersing action of the polymers causes the separation of dissolving oligomeric polyester components which disturbs the dyeing process. In the case of cellulose staining, the polymers according to the present invention promote the solubility of the reactive and direct dyes, and result in a better uniformity of the colorant on the fibers or in particular when large quantities of salts are present in the cellulose. the liquor In vat dyeing, it can advantageously be used as saponification or dye filling agents or as dispersants in the pigmentation bath. In the sulfur stain they support the dispersion of the dye and prevent tanning. In the staining of synthetic fibers, the polymers according to the present invention prevent the formation of agglomerates of disperse dyes, thus avoiding depositions in the cones. When the vat dyes and prints are washed, the polymers according to the present invention are bound to the unfixed dye components, and the redeposition is reduced to a considerable degree. Due to the increased diffusion of the dye towards the wash liquor, the polymers provide an optimal removal of the unfixed dyes with a saving of water and energy.

For this reason, the products of the present invention represent an effective substitute for polyphosphates in the subsequent treatment of naphthol dyes; When the reactive impressions are washed, it is prevented that the calcium alginate precipitates. The action of dispersion and complexation of the products according to the present invention takes effect without remobilizing the heavy metal compounds, both the dye chromophores, (reactive dyes and metal complexes) and deposits of natural and industrial origin that are Insoluble in water as such. In comparison with conventional auxiliary agents, such as polyacrylates, the required amounts can be reduced in practice approximately three to five times. The polymers according to the present invention can be used in combination with surfactants, in particular anionic detergents in non-neutralized (acidified) form in combination with organic complexing acids, such as citric acid, lactic acid, gluconic acid and phosphonic acids and surfactants, in particular anionic detergents. For example, such combinations are advantageously used in place of the conventional multistage pretreatment carried out in the separation baths; for example, in such a way that the pretreatment is carried out in only an adjustable treatment bath under the addition of the polymers according to the present invention to treat cotton or high-loaded cotton wool, this usually includes the extraction steps with acid, bleached with chlorite, boiled and blanched with H202. This method according to the present invention can also be used in continuous processes. The methods prevent the formation of undesirable organic halogen compounds that imply the respective environmental impact. The polymers are suitable additives for desizing fiber sizes which are sensitive to water hardness, for example, polyester sizes. The polymers according to the present invention exhibit good to excellent activity as auxiliary agents in the manufacture of leather when it is used, among other processes in the processes of soaking, liming, washing after liming, and in the desapelambramiento with lime, in particular, in the desapelambramiento with C02. In chrome tanning they cause an increased chromium absorption through the leather, the polymers of the present invention have average molecular weights of less than 5,000 g / mol being particularly preferred. In retanning the polymers according to the present invention give fullness and softness to the leather; Particularly preferred are copolymers having portions of 0.5-10% by weight of the monomers according to e) which have a hydrophobic effect or produce a character similar to the surfactant. Due to their dispersion and heavy metal complexation but not property remobilization, the polymers according to the present invention can also be advantageously used as auxiliary agents in papermaking. For example, in the production of pigment dispersions and fillers, such as kaolin, calcium carbonate, white satin, talcum, titanium dioxide, aluminum hydroxide, and barium sulfate, as well as the production of coating colors. Therefore the filler and pigment suspensions as well as the coating colors have a high solids content and high storage stability is obtained. The polymers according to the present invention can be used in combination with other auxiliary agents. The high molecular weight polymers are suitable for other purposes, for example, as thickeners, papermaking auxiliaries, auxiliaries in the treatment of water and wastewater, or as additives for drilling fluids.

The production and properties of the polymers according to the present invention will be illustrated in greater detail in the following examples. Specific application tests show the high effectiveness of polymers in the inhibition of water hardness, the excellent binding capacity of Ca2 + / Fe3 + or the dispersion of pulverized CaC03, the complexation of heavy metals at different temperatures and pH values, as well as the very good ability to drag stains or dirt in the dragging processes (suspension capacity) hydrophilic). In addition to the dispersion of the pigment, its application in the manufacture of leather is exemplary in the retanning, and chemical finishing of textiles, is exemplary in the stabilization of bleaching baths, in the staining and dispersion.

Preparation Examples Example 1 In a glass polymerization reactor equipped with heating bath, precision glass stirrer, liquid substance dosing devices, and reflux condenser, were placed 114.8 g of maleic anhydride, 2.97 g of sodium methallyl sulfonate, and 12.6 mg of iron sulphate (II) and ammonium in 283.2 g of demineralized water. 168.5 g [50% by weight] of sodium hydroxide solution was added to this mixture which was heated to 90 ° C until a clear solution resulted. Starting at the same time, two solutions were dosed to this preparation during a period of 4 hours. Solution I consisted of 146.5 g of acrylic acid, 35.4 g of vinyl acetate, 65.1 g [50% by weight] of sodium hydroxide solution, and 45.0 g of demineralized water. Solution II consisted of 50.55 g [35.5% by weight] of hydrogen peroxide, 4.0 g of sodium peroxodisulfate, and 35.0 g of water. After the end of the dosage, stirring was continued at 90 ° C for another 60 minutes; 31 g of the aqueous phase were then distilled off from the bath via the distillation connection tube. Cooling to 40 ° C, fixing to pH 10 using 54.8 g [50% by weight] of sodium hydroxide solution, refluxing for 3 hours. The light yellow, clear, cooled solution was fixed at a pH of 6.8 by means of 46.5 g of concentrated hydrochloric acid. The final product had a solids content of 39.0%, the molecular weight was approximately Pm = 12,000 g / mol.

Example 2 Again as in Example 1, the quantities prepared or dosed in the reactor were changed as follows: Loading: 229.6 g of maleic anhydride, 450.6 g of water, 337.0 g [50% by weight] of sodium hydroxide solution, 12.2 g of sodium methallyl sulfonate, and 25.2 mg of iron (III) sulfate and ammonium. Feeding solution I: 293.0 g of acrylic acid, 90 g of water, 130.2 g [50% by weight] of sodium hydroxide solution, and 70.8 g of vinyl acetate. Feed solution II: 8.0 g of sodium peroxodisulphate 8.0 g, 135.2 g of [35% by weight] of hydrogen peroxide in 81.8 g of water. After the end of the dosage, stirring was continued for 30 minutes, then 56.1 g of liquid were distilled. The saponified and neutralized polymer with a solids content of 43.1% has a viscosity of 540 mPa.s. The molecular weight is in the range of Pm = 11,000 g / mol.

Example 3 Modification of Example 1, the following amounts were prepared or dosed: Loading: 114.8 g of maleic anhydride, 283.2 g of water, 168.5 g [50% by weight] of sodium hydroxide solution, 8.91 g of sodium methallyl sulfonate, and 12.6 mg of iron (III) sulfate and ammonium. Feed solution I: 146.5 g of acrylic acid, 45.0 g of water, 65.1 g [50% by weight] of sodium hydroxide solution, and 35.4 g of vinyl acetate. Feed solution II: 50.6 g [35% by weight] of hydrogen peroxide, 4.0 g of sodium peroxodisulfate in 35.0 g of water. After completion of the dosing and a stirring time of 30 minutes, 36.1 g of the aqueous phase was distilled via the distillation connection tube and the still weakly acidic polymer solution (pH 5.2) was refined for 6 hours. After neutralization a polymer solution was obtained which had a solids content of 41.6% and which comprises 0.10% fumaric acid plus 0.03% maleic acid. The molecular weight was Pm = 10,200 g / mol.

Example 4 Example 2 was repeated with the following changes: Loading: 229.6 g of maleic anhydride, 31.3 g of sodium methallyl sulfonate, 337.0 g [50 wt.%] Of sodium hydroxide solution, and 25.2 mg of iron (II) sulfate and ammonium in 450.6 g of demineralized water. Feeding solution I: 293.0 g of acrylic acid, 70. 8 g of vinyl acetate, 130.2 g [50% by weight] of sodium hydroxide solution, and 90.0 g of water. Feed solution II: 8.0 g of sodium peroxodisulfate, 135.2 g [35% by weight] of hydrogen peroxide and 81.8 g of water. After finishing the dosing and a stirring time of 30 minutes, 1 g of vinyl acetate and 55 g of the aqueous phase of the bath were distilled. The saponified and neutralized polymer had a solids content of 42.4% and a viscosity of 430 mPa.s.

Example 5 The manufacture of Example 5 corresponding to that of Example 2. The quantities prepared or dosed in the reactor changed as follows: Loading: 229.6 g of maleic anhydride, 66.0 g of sodium methallyl sulfonate, 337.0 g [50% by weight] of sodium hydroxide solution, and 25.2 mg of iron sulphate (II) and ammonium in 490.0 g of water.

Feeding solution I: 293.0 g of acrylic acid, 70. 8 g of vinyl acetate, 130.2 g [50% by weight] of sodium hydroxide solution, and 90.0 g of water. Feed solution II: 8.0 g of sodium peroxodisulfate, 135.2 g [35% by weight] of hydrogen peroxide and 81.8 g of water. Once the dosing was finished, stirring was continued at 90 ° C for another 30 minutes, and distilled 52. 9 g of aqueous phase via the distillation connection tube. The clear saponified and neutralized polymer solution had a content of 44.1% and a molecular weight of Pm = 10,000 g / mol.

Example 6 In a polymerization test according to the specification for the preparation of Example 2, the following quantities were prepared or dosed: Loading: 91.8 g of maleic anhydride, 59.3 g of sodium methallyl sulfonate, 134.8 g [50% w / w solution of sodium hydroxide, and 12.6 mg of iron (II) sulphate and ammonium in 225.3 g of water. Feed solution I: 117.2 g of acrylic acid, 23.3 g of vinyl acetate, 52.1 g [50% by weight] of sodium hydroxide solution, and 45.0 g of water.

Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After finishing the dosage and stirring at 90 ° C for another 30 minutes, 30.5 g of aqueous phase was distilled. The saponified and neutralized polymer had a solids content of 41.2% and a molecular weight of Pm = ,500 g / mol.

Example 7 The production of Example 7 was carried out in correspondence with Example 2. The quantities prepared and dosed to the reactor were changed as follows: Loading: 229.6 g of maleic anhydride, 11.24 g of sodium methallyl sulfonate, 337.0 g [50% by weight] of sodium hydroxide solution, and 25.2 g of iron (II) sulfate and ammonium and 460.0 g of water. Feeding solution I: 293.0 g of acrylic acid, 27.6 g of vinyl acetate, 130.2 g [50% by weight] of sodium hydroxide solution, and 90.0 g of water. Feed solution II: 8.0 g of sodium peroxodisulfate, 135.2 g [35% by weight] of hydrogen peroxide and 81.8 g of water. After dosing and a stirring time of 30 minutes, 49.8 g of the aqueous phase of the batch were distilled. The saponified and neutralized polymer solution had a solids content of 37.1%, the average molecular weight was Pm = 6,500 g / mol.

Example 8 Except for 29.0 g of sodium methallyl sulfonate, the operation of this test corresponds to that of Example 7.

The clear polymer solution had a solids content of 41.2%, a viscosity of 310 Mpa.s., and a molecular weight of Pm = 6.000 g / mol.

Example 9 The production of Example 9 corresponds to that of Example 2. The quantities prepared or dosed to the reactor were changed as follows: Loading: 109.8 g of maleic anhydride, 29.7 g of sodium methallyl sulfonate, 161.1 g [50% by weight] of solution of sodium hydroxide, and 12.6 g of iron (II) sulphate and ammonium and 200.0 g of water.

Feed solution I: 142.4 g of acrylic acid, 14.8 g of vinyl acetate, 63.2 g [50% by weight] of sodium hydroxide solution, and 70.3 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. The saponified and neutralized product is clear and had a solids content of 42.6% and a viscosity of 340 mP.s.

Example 10 The production was carried out according to Example 2 with the following changes with respect to the amount: Loading: 44.5 g of maleic anhydride, 29.7 g of sodium methallyl sulfonate, 65.3 g [50% by weight] of sodium hydroxide solution sodium, and 12.6 g of iron (II) sulfate and ammonium and 170.3 g of water. Feed solution I: 207.7 g of acrylic acid, 14.8 g of vinyl acetate, 92.2 g [50% by weight] of sodium hydroxide solution, and 100.0 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After dosing and stirring for 30 minutes, 30.0 g of aqueous phase of the batch was distilled. The saponified and neutralized product had a solids content of 41.5% and a viscosity of 860 Mpa.s.

Example 11 Production method of Example 11 as in Example 2. The quantities prepared or dosed to the reactor were changed as follows: Loading: 44.5 g of maleic anhydride, 118.68 g of sodium methallyl sulfonate, 65.3 g [50% by weight] of solution of sodium hydroxide, and 12.6 g of iron (II) sulphate and ammonium and 240.0 g of water. Feed solution I: 118.68 g of acrylic acid, 14.8 g of vinyl acetate, 52.7 g [50% by weight] of sodium hydroxide solution, and 30.0 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After finishing the dosage, the batch was kept at 90 ° C for 30 minutes and then 28.2 g of aqueous phase were distilled. The saponified and neutralized product with a solids content of 43.8% had a viscosity of 95 mPa.s.

Example 12 In a polymerization experiment according to the formula of Example 2, the following amounts were prepared or dosed: Loading: 104.4 g of maleic anhydride, 44.5 g of sodium methallyl sulfonate, 153.3 g [50% by weight] of hydroxide solution of sodium, and 12.6 g of iron (II) sulphate and ammonium and 230.0 g of water. Feed solution I: 132.9 g of acrylic acid, 14. 8 g of vinyl acetate, 59.0 g [50% by weight] of sodium hydroxide solution, and 40.0 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After finishing the dosage, the batch was kept at 90 ° C for 30 minutes and then 30.3 g of aqueous phase were distilled. The saponified and neutralized polymer solution had a solids content of 42.4%.

Example 13 Production of Example 13 as in Example 2. The amounts prepared or dosed to the reactor were changed as follows: Loading: 125.2 g of maleic anhydride, 5.93 g of sodium methallyl sulfonate, 183.8 g [50% by weight] of sodium hydroxide solution, and 12.6 g of iron (II) sulphate and ammonium and 22.0 g of water . Feed solution I: 159.6 g of acrylic acid, . 9 g of vinyl acetate, 70.9 g [50% by weight] of sodium hydroxide solution, and 60.0 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After the dosing was finished, the temperature was maintained at 90 ° C for 30 minutes, and then 36.4 g of the aqueous phase of the batch were distilled. The saponified, neutralized and clear product solution with a solids content of 42.3% had a viscosity of 660 mPa.s.

Example 14 The production was carried out as in Example 2 with the following changes in the amounts: Loading: 121.4 g of maleic anhydride, 14.8 g of sodium methallyl sulfonate, 178.1 g [50% by weight] of sodium hydroxide solution, and 12.6 g of iron (II) sulphate and ammonium and 225.0 g of water.

Feed solution I: 154.6 g of acrylic acid, 5.9 g of vinyl acetate, 68.6 g [50% by weight] of sodium hydroxide solution, and 45.0 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. The saponified, neutralized and clear product solution with a solids content of 42.1% had a viscosity of 360 mPa.s. The molecular weight was Pm = 8,000 g / mol.

Example 15 In a polymerization experiment according to the specification for the preparation of Example 1, the following amounts were prepared or dosed: Loading: 114.8 g of maleic anhydride, 29.7 g of sodium methallyl sulfonate, 168.5 g [50% by weight] of sodium hydroxide solution, and 12.6 g of iron (II) sulphate and ammonium in 225.0 g of water. Feeding solution I: 146.6 g of acrylic acid, . 9 g of vinyl acetate, 65.1 g [50% by weight] of sodium hydroxide solution, and 45.0 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After dosing and subsequent stirring for 30 minutes, 29.6 g of aqueous phase of the batch was distilled. The clear saponified polymer solution with a solids content of 42.0% had a viscosity of 330 mPa.s.

Example 16 The production of Example 16 was carried out as in Example 2. The quantities prepared or dosed to the reactor were changed as follows: Loading: 114.8 g of maleic anhydride, 14.8 g of amidopropanesulfonic acid, 168.5 g [50% by weight] of sodium hydroxide solution, and 12.6 g of iron (II) sulphate and ammonium and 225.0 g of water. Feeding solution I: 146.6 g of acrylic acid, . 4 g of vinyl acetate, 61.1 g [50% by weight] of sodium hydroxide solution, and 45.0 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After the end of the dosage, stirring at 90 ° C, the mixture was continued for another 30 minutes, and then 30.7 g of the aqueous phase of the batch were distilled. The saponified and neutralized polymer with a solids content of 41.9% had a molecular weight of Pm = 10,500 g / mol.

Example 17 In a polymerization experiment according to Example 2 the following quantities and components were prepared or dosed: Filler: 114.8 g of maleic anhydride, 168.5 g [50% by weight] of sodium hydroxide solution, and 12.6 g of sodium sulfate iron (II) and ammonium and 225.3 g of water. Feeding solution I: 146.6 g of acrylic acid, 35.4 g of vinyl acetate, 65.1 g [50% by weight] of sodium hydroxide solution, and 45.0 g of water, and 5.94 g [35% by weight] of sodium sulphonate vinyl. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After finishing the dosage, stirring was continued for 30 minutes at 90 ° C; 36.5 g of aqueous phase of the batch were distilled. The saponified and neutralized polymer with a solids content of 41.0% had a molecular weight of Pm = 10,300 g / mol.

Example 18 The manufacture of Example 18 was carried out as in Example 2. The amounts and components prepared or dosed to the reactor were changed as follows: Loading: 114.8 g of maleic anhydride, 6.1 g of sodium methallyl sulfonate, 6.1 g of allyl alcohol -10-EO, 168.5 g [50% by weight] of sodium hydroxide solution, and 225.3 g of water. Feeding solution I: 146.5 g of acrylic acid, . 4 g of vinyl acetate, 65.0 g [50% by weight] of sodium hydroxide solution, and 45.0 g of water. Feed solution II: 4.0 g of sodium peroxodisulfate, 67.6 g [35% by weight] of hydrogen peroxide and 40.9 g of water. After dosing and subsequent stirring for 30 minutes, 28.4 g of aqueous phase was distilled from the batch. The saponified and neutralized polymer solution with a solids content of 42.9% had a viscosity of 560 mPa. s.

Example 19 Example 2 was repeated with the exception that 1.8 of sodium dodecane sulfonate was placed in the form of a 20% solution in the reactor preparation. Compared to Example 2, the clear polymer solution to be obtained had a clearly reduced surface tension.

Example 20 The polymerization was carried out as in Example 2, however, the aggregated amounts of initiators were changed as follows: 10.6 g of sodium persulfate and 179.8 g [35% by weight] of hydrogen peroxide. A clear polymer of low viscosity was formed. The solids content was 42.9%.

Comparative Example 1 This comparative example describes the production of a polymer of fumaric acid and sodium methallylsulfonate according to the teachings of U.S. Patent No. 3,879,288. A mixture of 200 g of sodium methallyl sulfonate and 110 g of fumaric acid in 250 ml of demineralized water was placed in a 1 liter polymerization reactor equipped with a precision glass stirrer and internal thermometer.

The charge was heated to 90 ° C, and 5 ml [30% by weight] of hydrogen peroxide was added. One hour later, 5 ml [30% by weight] of hydrogen peroxide was added again and stirring was continued at 90 ° C for another two hours. A clear solution was obtained, which had a dry substance content of 53.6% and comprised 0.8% free fumaric acid and 7.4% free sodium methallyl sulfonate. With respect to the sodium methallyl sulfonate used, this corresponds to a conversion of 79%. This example clearly shows that the polymers manufactured according to US Pat. No. 3,879,288 have a considerably higher content of residual monomers than the polymers according to the present invention.

Comparative Example 2 The second comparative example is a terpolymer of maleic acid, acrylic acid and vinyl acetate; its production is described in German Patent DE 4300772, Example 1. 63.8 g of maleic anhydride, 260.0 g of demineralized water, 93.6 g [50% by weight] of sodium hydroxide solution and 6.3 mg of iron sulphate (II) and ammonium were placed in a 2 1 glass polymerization vessel and heated to 6 ° C. With a period of 4 and 4.5 hours, two solutions were dosed in the clear solution. Solution I (4 hours) is a mixture of 31.4 g of acrylic acid, 42.1 g of vinyl acetate and 100 g of water. The second solution (4.5 hours) consists of 18.7 g [35% by weight] of hydrogen peroxide and 100 g of water. At the end of the dosing of solution II, the internal temperature rose to 92 ° C; stirring was continued at this temperature for one hour, and 11 g of aqueous phase and 5 g of vinyl acetate were extracted by means of a water separator. At 40 ° C the batch was fixed at pH 10 by means of sodium hydroxide solution, refluxed for 60 minutes, and neutralized to pH 7 using hydrochloric acid. The average molecular weight of the polymer was Pm = 22,000 g / mol. The residual monomer content is in the order of 2530 ppm of maleic acid, 300 ppm of fumaric acid, 370 ppm of acrylic acid, < 10 ppm vinyl acetate.

Examples related to Application Technology Example 21 - Dispersing capacity of calcium carbonate An essential feature of coadditives in detergents and cleaners is the ability to prevent slightly soluble precipitations of alkaline earth or heavy metal salts which, for example, cause fouling on fabrics. To determine the dispersing capacity of calcium carbonate (CCDC) [according to Richter Winkler in Tenside Surfactants Detergents 24 (1987) pp 213-216] the procedure was as follows: 1 g of product (dry substance) was dissolved in 100 ml of distilled water, and 10 ml of 10% sodium carbonate solution was added thereto. A pH of 11 was set using sodium hydroxide solution, and the titration was carried out with 0.25 ml of calcium acetate solution until a first permanent turbidity occurred. The CCDC was indicated in mg of CaCO3 / g of dry substance. i n Example No. CCDC 1 334 2 287 15 3 318 4 291 277 7 378 Comparative Example 1 44 Comparative Example 2 273 Commercial Product (polymer based on maleic acid 258 / Na salt of acrylic acid) 25 Calcium carbonate dispersion tests show that the polymers according to the present invention provide better dispersing activity of CaCO3 and the comparative products in forms of commercial products or those manufactured according to the teachings of U.S. Patent No. 3,879,288 and DE 4300772 Al.

Example 22 - Hampshire Test: 2 ml of 10% sodium carbonate was added to a solution of 1 g of product (dry substance) in 100 ml of water, then the pH was set to 11 using hydrochloric acid or sodium hydroxide solution. The titration was carried out with 0.25 mol of calcium acetate solution until a first permanent turbidity occurred. The indication was given in mg of CaCO3 / g of dry substance: Example Hampshire? 563 2 525 3 540 4 566 5 588 6 646 7 547 8 601 9 616 10 689 Comparative Example 1 89 Comparative Example 2 478 The above Table shows that the polymers according to the present invention under the conditions of the Hampshire test have a high calcium binding capacity or a higher precipitation prevention capacity than the polymers obtained according to the teachings of the DE 4300772 Al and US 3,879,288.

Example 23 - Resistance to boiling hard water A certain amount of a 10% polymer solution was added to a calcium chloride solution (pure calcium hardness of 33.6 ° dH), heated on a heating plate for 5 minutes and subsequently judged for turbidity. By varying the amount of polymer, the concentration at which a clear solution was obtained for the first time was determined. The indication was given in grams per liter of hard water.

Example No. Hard water resistance I 2.0 10 1.5 II 1.5 Comparative Example 2 2.0 Commercial product based on maleic acid / acrylic acid copolymer 2.0 The results clearly demonstrate that the polymers according to the present invention can provide an effective inhibition of the scale of the boiler or similar deposits and that the precipitations of the components of the hard water can be prevented.

Example 24 - Effectiveness as an anti-deposition agent The fouling potential of the solutions forming deposits and the effectiveness of the anti-deposition agents on the formation of scale was examined in a dynamic method. The pressure changes caused by the formation of deposits in a spirally wound capillary tube which was placed in a heating bath and the flow through the deposit forming solution was measured as well as the change in the hardness in the forming solution of deposits by means of complexometric titration. The inhibition value results from the ratio of hardness, current to the initial hardness of the test solution; and the speed at which the deposits are formed results from the change in pressure depending on the dose of the anti-deposition agent.

Example of Amount of anti-exposure agent [ppm] Polymer 35 25 20 15 10 7.5 5% inhibition 11 100 100 100 100 100 100 95 6 100 100 100 100 98 Compound of Example 2 86 Commercial product 92 of maleic acid / acrylic acid The measured values show that the polymers according to the present invention have a higher efficiency in this practical test than those of Comparative Example 2 (according to DE 43 00 772 Al) and that of commercial products based on maleic acid / acrylic acid Example 25 - Iron / Manganese Bonding Capacity Graded amounts of iron (III) chloride solution 0.25 mole in various series of 5 tests were added to complexing agent solutions consisting of 2.5 ml of a 10% product solution in 150 ml of demineralized water, these were filled then up to 250 ml with demineralized water. In the first test series the pH was fixed at 7 using 10% sodium hydroxide solution, in the second test series the pH was fixed at 11. The samples were then left at room temperature and at 95 ° C for a defined period of time followed by visual judgment for precipitation formation. The test period is 3 hours at room temperature and 1 hour at 95 ° C, after of having reached the test temperature. The concentration at which a clear solution was obtained for the first time was determined. The indication was given in mg of iron per gram of polymer.

Z ° .0 Example No. pH 7 / rt pH 11 / rt pH 7/95 ° C pH 11/95 ° C 2 394 1432 473 1145 4 597 1250 611 1264 5 688 1225 696 1225 Example Comp. 2 288 1511 324 576 The above Table shows that the polymers according to the present invention have a significantly higher iron binding capacity under all test conditions - with the exception of pH 11 / rt - than the products described in DE 4300772 Al. Tests using a manganese (II) salt solution of the same concentration also resulted in an excellent binding capacity of the polymers according to the present invention compared to the products according to DE 43 00 772 A1.

Example 26 - Hydrophilic Suspension Capacity The main task of a co-additive in the detergent is - in addition to preventing precipitation - the dispersion of hydrophilic grime particles in the wash liquor.

This prevents the dirt from being separated from the fiber during the washing of the redeposition on the washed items. (anti-redeposition property). These co-additive characteristics which is called anti-redeposition power can be determined, for example, by means of the hydrophilic suspension capacity for pulverized iron oxide. Prior to the effective date of the "Regulation on the maximum amounts of phosphates in detergent", phosphate salts were used as sole additives due to their excellent suspension properties.

The hydrophilic suspension capacity was determined by measuring the photometric turbidity of a suspension consisting of a test substance, an iron oxide pigment, and the MARLON A surfactant (alkyl benzene sulfonate by Hüls AG, Mari, FRG). In a 25 ml mixing cylinder, powdered Fe203 (c = 40 g / 1) was dispersed homogeneously in an aqueous solution of the test substance (c = 2 g / 1) under addition of MARLON A (c = 1 g) /1) . 24 hours later, 1 ml of solution was withdrawn by means of a 1 ml syringe at the height of the 1 ml mark; this solution was diluted with 39 ml of demineralized water, stirred again, and the remaining turbidity was determined photometrically. The E450 extinction at 450 nm was measured in a 1 cm cuvette. The smaller the dispersion of the deposits during storage, the greater the extinction values measured and the greater the hydrophilic suspension capacity. Sodium triphosphate was used as a comparative substance. Example Extinction E450 2 50 6 135 Comparative Example 2 Maleic acid / acrylic acid copolymer, commercial product sodium triphosphate 160 The results prove that the polymers according to the present invention - as compared to the polymers of DE 4300772 Al and the commercial acrylic acid / maleic acid copolymers have a clearly advantageous activity with respect to the dispersion of the hydrophilic particles. By using the polymers according to the present invention it is also possible more surprisingly to be close to the effective effective range of sodium triphosphate.

Example 27 - Use of the products according to the present invention as bleached stabilizers In the following test, the applicability of the polymers according to the present invention as bleach stabilizers in the bleaching of raw fibers in viscous bleaching was exemplarily demonstrated. The bleaching process is comprised of the desizing, acid extraction and bleaching steps; Your special requirements will be described later. The measurement of the amount of bleach stabilizers is the whiteness reached by the products (according to Berger) on the one hand, and the content of residual hydrogen peroxide in the liquor, measured by titration with KMn04 solution n / 10, by other side.

Stabilizing composition: Active substance [%] prod. 1 prod. 2 prod. 3 lactic acid: 80 12% 12% 12% gluconic acid: 50 27% 27% 27% Example 2: 40 61% - - Example 4: 40 - 61% - Example 5: 40 - - 61% 100% 100% 100% A. Depressed [acrylate sizing] Formulation: liquor ratio: 1:20 2 g / 1 of new Sulfaton UNS (commercial product of Che ische Fabrik Stockhausen, Krefeld) Sodium hydroxide solution 1 g / 1 [50% by weight] The complete material to be bleached is treated in the desprestado bath at 80 ° C for 60 minutes, and then rinsed with hot and cold water.

B. Extraction with acid In the extraction with acid one of each of the three product mixtures mentioned above (products 1-3) at a concentration of 0.5 g / 1 as well as concentrated hydrochloric acid (c = 1 ml (l) were added to the desized material (tests 1-3) at a liquor ratio of 1:20, At the same time, a comparative sample which did not contain a stabilizer was extracted acidically (test 4). -50 ° C for 20 minutes and then rinsed cold.

C. Bleaching The bleaching was carried out under the following conditions in the following steps: liquor ratio 1:20 heating 3 ° C / minute 45 minutes at 95 ° C cooling titration of the residual peroxide with KMn04 n / 10 rinse: hot and cold The composition of the individual bleaching baths can be observed in the following Table.

Bleaching bath 1 2 3 4 product 1 g / i 0.5 - -product 2 g / i - 0.5 '-product 3 g / i - - 0.5 MgCl2.6H20 g / i 0.4 0.4 0.4 0.4 NaOH [50% by weight] g / i 4 4 4 4 H202 [35% by weight] g / i 8 8 8 8 residual peroxide% 33 30 40 21 whiteness (from 83 83 83 84 according to Berger) The above Table shows that a good degree of whiteness was achieved with all the products according to the present invention. Furthermore, the comparison of the amounts of residual peroxide from tests 1-3 with test 4 clearly shows that all the products according to the present invention have a stabilizing effect on the bleaching agent and therefore ensure a moderate bleaching - as it is known to one skilled in the art. In addition, the high residual peroxide content in tests 1-3 shows that a sufficient amount of peroxide is always present during bleaching, even in the case of different raw fiber qualities.

Example 28 - Staining and Dispersion The raw cotton clothes were boiled with 5 ml of acetic acid at a ratio of 1:10 liquor for 30 minutes. Subsequently, 200 ml of liquor was cooled to 60 ° C and each of the following was added: 0.5 g / 1, 1.0 g / 1 and 2 g / 1 of polymer according to Example 2 0.05 g / 1 of indanthrene blue BC Coil 20.0 ml / 1 NaOH, 50%, and 5.0 g / 1 hydrosulfite, concentrate. After a residence time of 15 minutes (at 60 ° C), the liquor was sucked by means of a "Blauband filter" (blue band filter) and visually evaluated. The polymers showed a good dispersing activity; in the concentrations used, they prevent the precipitation of flocculates.

Example 29 - Washing the dyeing material At a liquor ratio of 1:20 and at a temperature of 70 ° -80 ° C the PES flakes dyed black were treated with a liquor of 1 g / 1 of polymer according to Example 2 and 1 g / 1 of SOLOPOL DP (ethoxylated fatty amine, commercial name of Chemische Fabrik Stockhausen GmbH, Krefeld) for 20 minutes; then it was subjected to hot and trio rinse. Oligomers, color and fiber dust were removed from the fibers to a large extent.

Example 30 - Leather Manufacturing In the following it is shown that the polymers according to the present invention are suitable for the leather manufacture; Retanning / greasing leather was used as an example. The softness of the leather, tight grain and fullness or amplitude are used as evaluation criteria. The polymers according to Examples 2, 4, 5 were tested with good results in comparison with a commercial retanning agent based on polyacrylic acid / acrylamide and a polymer according to Comparative Example 2. These good results show the suitability of the polymers according to the present invention in the manufacture of cuer.

Retanning / greasing leather sequence: Material: wet blue, thickness: 1.8-2.0 mm The following indications in% are related to the shaved weight.

Retannage: 200.0% water 45 ° C 2.0% Chromosal "B1 '2.0 Brancorol5 * B" not dissolved 60 min.

Drained bath, separate leather Neutralization: 100.0% water 35 ° C 1.0% sodium formate undissolved 30 min. 0.5% sodium bicarbonate 1:10 60 min. pH: 5.0 Retanning / Staining: 1.1% active substance 1: 3 polymer 3.0% MimosaJ undissolved 3.0% Tanigan® OS4 not dissolved 30 min. 1.0% Baygenal * Braun laNR5 1:20, hot 30 min.

Drained bath Rinse; water 60 ° C 10 min.

Grease 100% water 60 ° C Leather: 7.0% Coripol * RSb) 1: 4 2.0% Coripol * NZN "60 ° C 60 min 1.5% formic acid 1: 5 30 min Final pH value: 3.1 - 3.3 Leather mounted during overnight, stretched, vacuum dried at 75 ° C / 2 min., conditioning, stacking 1: basic chromium (III) salt, 2: chromium salt (III) / organic fixing agent, 3: natural tanning agent of mimosa extract, 4: neutral tanning agent, Sintano, 5: brown coloring, 6: fatliquoring agent of natural and synthetic fats, 7: mixture of natural fat and lanolin.

Polymer according to Example Polymer 2 4 5 Comp. 2 C reative test: NI N2 N3 N4 softness * 2- 2-3 tightness of grain * 2-3 2-3 3 3 brown tone slightly slightly brown more gray than N4 than N4 Polymer according to Example Polymer 2 4 5 Comp. 2 Canercial retanning test: N5 N6 N7 N8 softness * 2- 3 2-3 2-tight grain * 2 2 2-3 2-tone brown slightly slightly brown darker brown than yellowish N4 * Priority evaluation 1 - 6, with 1 being the best Example 31 - Dispersion tests To demonstrate the dispersibility of the copolymers according to the present invention on pigment suspensions, talc (Finntalc CIO by OMYA) was stirred in aqueous copolymer solutions of pH 12 until a pigment content of 66% was reached, the viscosity immediately and 7 days later; the agitation capacity was graded with 1-6. The combination of POLYSALZ S / LUMITEN P-T (by BASF AG) was used as prior art. The addition of the dispersing agent was 0.2% / dry pigment abs., And in the case of POLYSALZ / LUMITEN the usual concentrations were used: 0.15 / 1.0% / dry pigment abs. The polymers according to the present invention of Examples 6 and 11 were tested and shown to be stable at slightly lower viscosities during the measurement period with a good to satisfactory stirring capacity. For this reason they are absolutely suitable for this purpose.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (56)

1. Water-soluble polymers suitable for laundry detergents and cleaners of polymerized monoethylenically unsaturated dicarboxylic acids, and / or their salts, monoethylenically unsaturated monocarboxylic acids, polymerized, and / or their salts, monoethylenically unsaturated monomers to which, after hydrolysis or Saponification can be converted into monomer units having one or more hydroxyl groups covalently bonded to the CC chain, and polymerized, the monoethylenically unsaturated monomers comprising sulphonic acid groups, sulfate groups, and optionally further polymerized, monomers copolymerizable by radicals, characterized in that from a) 10-70% by weight of C4-8 monoethylenically unsaturated dicarboxylic acids and / or their salts b) 20-85% by weight of C3-10 monoethylenically unsaturated monocarboxylic acids and / or their salts c) 1 - 50% by weight of monomers mo unsaturated which, after hydrolysis or saponification, can be converted into monomeric units having one or more hydroxyl groups covalently linked to the CC chain, and d) 0.1-40% by weight of monoethylenically unsaturated sulfonic acid groups or monomers containing sulfate groups or their salts, e) 0-10% by weight of monomers copolymerizable by additional free radicals, with the sum of the monomers according to a) to e) being 100%, by radical polymerization and acid hydrolysis or alkaline saponification in aqueous medium.

2. Water-soluble polymers suitable for use in laundry detergents and cleaners, according to claim 1 and 2, characterized in that they are composed of a) 10-70% by weight of dicarboxylic acids of monoethylenically unsaturated C-β or their salts b 20 - 85% by weight of monoethylenically unsaturated C3-10 monocarboxylic acids or their salts c) 1-50% by weight of monounsaturated monomers which, after hydrolysis or saponification, can be converted into monomer units having one or various hydroxyl groups covalently linked in the CC chain, and d) 0.1-40% by weight of monoethylenically unsaturated sulphonic acid groups or monomers containing sulfate groups or their salts, e) 0-10% by weight of additional free copolymerizable monomers , with the sum of the monomers according to a) to e) being 100%.

3. The water-soluble polymers suitable for laundry detergents and cleaners according to claims 1 and 2, characterized in that they consist of a) 20-60% by weight of C- dicarboxylic acids. monoethylenically unsaturated or their salts b) 25-65% by weight of C3- [alpha] or monoethylenically unsaturated monocarboxylic acids or their salts c) 1-30% by weight of monounsaturated monomers which, after hydrolysis or saponification, can be converted in monomeric units having one or more hydroxyl groups covalently bonded to the CC chain, and d) 0.5-25% by weight of monoethylenically unsaturated monomers comprising sulphonic acid groups or sulfate groups e) 0-10% by weight of copolymerizable monomers per additional radicals, with the sum of the monomers from a) to e) being 100%.

4. Water-soluble polymers suitable for laundry detergents and cleaners according to claims 1 to 3, characterized in that they consist of a) 25-55% by weight of monoethylenically unsaturated C-8 dicarboxylic acids or their salts b) 30 - 60% by weight of monoethylenically unsaturated C3-m monocarboxylic acids or their salts c) 1-20% by weight of monounsaturated monomers which, after hydrolysis or saponification, can be converted into monomer units having one or more hydroxyl groups covalently linked in the chain of CC, and d) 10% by weight of monoethylenically unsaturated monomers comprising sulphonic acid groups or sulfate groups e) 0-10% by weight of copolymerizable monomers by additional radicals, with the sum of the monomers of ) ae) being 100%.

5. Water-soluble polymers suitable for laundry detergents and cleaners according to claims 1 to 4, characterized in that they are composed of a) 25-55% by weight of C4-8 monoethylenically unsaturated dicarboxylic acids or their salts b) 30 - 60% by weight of monoethylenically unsaturated C3-10 monocarboxylic acids or their salts c) 1-15% by weight of monounsaturated monomers which, after hydrolysis or saponification, can be converted into monomer units having one or more hydroxyl groups covalently linked in the chain of CC, and d) 1-5% by weight of monoethylenically unsaturated sulphonic acid groups or monomers containing sulfate groups, and eg 0-10% by weight of copolymerizable monomers by additional radicals, with the sum of the monomers according to a) ae) being 100%.

6. Water-soluble polymers suitable for use in laundry detergents and cleaners according to claims 1-5, characterized in that they comprise maleic acid, itaconic acid and fumaric acid or their salts as monomeric component a), acrylic or methacrylic acid or their salts as the monomeric component b), vinyl acetate, vinyl propionate, ethylene glycol monovinyl ether, vinylene carbonate, and / or methyl vinyl ether as monomer component c), and (meth) allyl sulfonic acid, (meth) allyl alcohol sulfate sulfate (meth) hydroxyethyl acrylate, vinyl sulfonic acid, acrylamidomethylpropane sulfonic acid or its salts as monomeric component d).

7. Water-soluble polymers suitable for use in laundry detergents and cleaners according to claims 1 to 6, characterized in that they comprise maleic acid or its salts as monomer component a), acrylic acid or its salts as monomeric component b), acetate vinyl as monomeric component c), and (meth) allyl sulfonic acid or its salts as monomeric component d).

8. A process for the production of water-soluble polymers suitable for laundry detergents and cleaners according to claim 1 of monoethylenically unsaturated dicarboxylic acids and / or their salts and / or dicarboxylic acid anhydrides, monoethylenically unsaturated monocarboxylic acids and / or their salts , monoethylenically unsaturated sulfonic acid groups or monomers containing sulfate groups or their salts, and monoethylenically unsaturated monomers which, after acid hydrolysis or alkaline saponification, can be converted into monomer units having one or more hydroxyl groups covalently attached to the chain of DC, and optionally monomers copolymerizable by additional radicals, characterized in that they are formed by radical polymerization and hydrolysis or saponification in aqueous medium.

9. The process for the production of water-soluble polymers suitable for laundry detergents and cleaners according to claim 8, characterized in that the polymerization is carried out in aqueous solution at 40-180 ° C, preferably at -120 ° C. C.

10. The process for the production of water soluble polymers suitable for laundry detergents and cleaners according to claims 8 and 9, characterized in that the dicarboxylic acids, dicarboxylic acid anhydrides, and at least a partial amount of the monomers comprising acidic groups Sulphonic or sulfate are prepared together in the reaction vessel, because the remaining monomers are added during the polymerization, and because the polymerization is optionally carried out in a closed polymerization reactor.

11. The process for the production of water-soluble polymers suitable for laundry detergents and cleaners according to claims 8 to 10, characterized in that the dicarboxylic acid anhydride is hydrolyzed and at least partially neutralized before polymerization.

12. The process for the production of water-soluble polymers suitable for laundry detergents and cleaners according to claims 8-11, characterized in that the maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and fumaric acid or its salts are used as a monomer component a), acrylic or methacrylic acid or its salts are used as monomeric component b), vinyl acetate, vinyl propionate, ethylene glycol monovinyl ether, and / or methyl vinyl ether are used as monomeric component c), and (meth) allylsulfonic acid, (meth) allyl alcohol sulfate, vinyl sulfonic acid, hydroxyethyl (meth) acrylate sulfate, acrylamidomethylpropane sulfonic acid or its salts are used as the monomeric component d).

13. The process for the production of water-soluble polymers suitable for use in laundry detergents and cleaners according to claims 8 to 12, characterized in that the saponification is carried out with alkaline hydroxides in the presence of hydrogen peroxide, or with dioxide Sulfur after polymerization.

14. The process according to claims 8-13, characterized in that the polymerization is carried out in the presence of surfactant compounds.

15. The process according to claim 14, characterized in that the polymerization is carried out in the presence of anionic detergents and / or not

16. The process according to claim 14, characterized in that the polymerization is carried out in the presence of 0.1-5% by weight, preferably 0.5-2% by weight of surfactant compounds.

17. The use of the polymers according to claims 1-13 as additives or co-additives in detergents.

18. The use of the polymers according to claims 1-13 in combinations of additives.

19. The use of the polymers according to claims 1-13 as additives or co-additives in zeolite-free detergents.

20. The use of the polymers according to claims 1-13 as additives or co-additives in phosphate-free or low-phosphate detergents.

21. The use of the polymers according to claims 1 - 13 as binders for multivalent metal ions.

22. The use of the polymers according to claims 1 - 13 as additives in cleaning agents.

23. The use of the polymers according to claims 1 - 13 as auxiliary agents in textile finishing.

24. The use of the polymers according to claims 1-13 in the pretreatment of raw fiber materials or textile materials, in particular in boiling, cleaning and bleaching in an autoclave.

25. The use of the polymers according to claims 1 - 13 as bleach stabilizers.

26. The use of the polymers according to claims 1 - 13 as additives or washing aids in the dyeing process.

27. The use of the polymers according to claims 1-13 as auxiliary agents in textile printing, in particular in the washing of reactive prints and vat colors of natural and / or synthetic or textile fibers.

28. The use of the polymers according to claims 1-13 as additives in textile fiber sizes.

29. The use of the polymers according to claims 1-13 as auxiliary agents in the desizing of natural or synthetic or textile fibers.

30. The use of the polymers according to claims 1-13 as auxiliary agents according to claims 24-28, characterized in that they are used in combination with surfactants, in particular anionic agents.

31. The use of the polymers according to claims 1-13 as auxiliary agents according to claims 24-28, characterized in that they are used in combination with complexing carboxylic acids.

32. The use of the polymers according to claims 1-13 as auxiliary agents according to claims 24, 25, 30, 31, characterized in that they are used in chlorite-free bleaching, preferably in multi-step processes in a bath Adjustable treatment or in continuous processes.

33. The use of the polymers according to claims 1 - 13 as auxiliary agents in the manufacture of leather.

34. The use of the polymers according to claims 1 - 13 as auxiliary agents in the manufacture of leather during soaking, scaling with lime, in particular in washing processes after liming with lime and in particular in lime scale removal and unleaded with lime with

35. The use of the polymers according to claims 1 - 13 as additives in pretanning, tanning and retanning.

36. The use of the polymers according to claims 1-13 for the inhibition of water hardness as anti-deposition agents.

37. The use of the polymers according to claims 1-13 as dispersing agents.

38. Detergents or cleaners, in particular laundry detergents, characterized in that they comprise the polymers according to claims 1-13.

39. Detergents or cleaners, in particular laundry detergents, according to claim 38, characterized in that they comprise 0.5-30% by weight, preferably 2-25% by weight of polymers according to claims 1 - 13, 0-20 % by weight, preferably 5-15% by weight of inorganic carbonates, and 0-20% by weight, preferably 5-15% by weight of salts of organic polycarboxylic acids.

40. The compound according to claims 38 and 39, characterized in that it comprises as additives 10-65% by weight of zeolite and / or crystalline layered silicates, and 2-20% by weight of polymers according to claims 1-13.

41. The compound according to claims 38 to 40, characterized in that it comprises 2-7% by weight of amorphous silicates.

42. The compound according to claims 38-41, characterized in that it comprises 10-40% by weight of surfactants, 0-5% discoloration inhibitors, and 15-45% by weight of usual additional ingredients for detergents, and because it has a apparent density of 300 to 1,200 g / 1, in particular of more than 600 g / 1.

43. The compound according to claims 38-42, characterized in that it is free of phosphate and / or zeolite and / or layered silicate.

44. An additive combination, characterized in that it comprises the polymers according to claims 1-13.

45. The additive combination according to claim 44, characterized in that it comprises 50-70% by weight, preferably 55-65% by weight of zeolite or crystalline layered silicates, in particular zeolite or crystalline layered silicates in the weight ratio of 1: 1 or more, and 1 to 30% by weight of polymer according to claims 1-13.

46. The combination of additives according to any of claims 44 and 45, characterized in that it comprises 5 to 30% by weight, preferably 5 to 25% by weight of sodium carbonate, 0 to 10% by weight, preferably 2 to 8% by weight of amorphous silicates, 0-8% by weight, preferably 0.5-5% by weight, and in particular up to 2% by weight of usual (co) polymeric acrylates, and 0 to 25% by weight, preferably 2 to 20% by weight, and in particular 5-20% by weight of salts of organic polycarboxylic acids.

47. The additive combination according to any of claims 44 to 46, characterized in that it comprises liquid or wax-like components, preferably non-ionic detergents.

48. A process for the production of an additive combination according to claims 44 to 47 or a detergent or cleaning agent according to claims 38-43, characterized in that the granular material is produced by spray drying, or by a mixing process, granulation and / or extrusion.

49. Cleaners for hard surfaces, characterized in that it comprises 1-60% by weight of polymer according to claims 1 - 13, 5 - 90% by weight, preferably 5 - 70% by weight of alkali formers, 0 - 60% by weight, preferably 5-50% by weight of dispersing and complexing agents, 0-10% by weight, preferably 0.5-5% by weight of low-foam surfactants, and 0 50% by weight of additional customary additives .

50. The compounds according to claim 49, characterized in that the alkali formers are selected from the group consisting of alkali metal hydroxides, alkali metal carbonates and alkali metal carbonates.

51. The compounds according to claims 49 and 50, characterized in that the dispersing and complexing agents are selected from the group consisting of citrates, phosphonates, homo- and copolymers of acrylic acid, isoserin diacetic acid, polyasparginic acids, ethylenediaminetetraacetic acid and triacetic nitrile acid .

52. The compounds according to claims 49-51, characterized in that the low-foam surfactants are selected from the group of non-ionic detergents.

53. The compounds according to claims 49-52, characterized in that they comprise 0. 5-20% by weight of oxygen-based bleaching agents and 0-10% by weight of bleach activators.

54. The compounds according to claims 49-53, characterized in that they comprise 0. 1 - 5% by weight of enzymes.

55. The compounds according to claims 49-54 in liquid, pulverized, granulated or tablet form.

56. A process for the production of a compound according to claim 55, characterized in that the agent is produced by spray drying and / or by mixing, granulating and / or extruding processes. SUMMARY OF THE INVENTION The present invention relates to water-soluble polymers consisting of a) monoethylenically unsaturated dicarboxylic acids and / or their salts, b) monotyphenyl unsaturated monocarboxylic acids and / or their salts, c) monounsaturated monomers which, after hydrolysis or Saponification can be converted into monomers having a hydroxyl group covalently linked to the CC chain, d) monomers containing sulphonic acid groups or monoethylenically unsaturated sulfate groups, and optionally e) monomers copolymerizable by additional radicals, with the sum of the monomers from a) to e) being 100%. The present invention also relates to a process for the production of these polymers by radical polymerization and hydrolysis in aqueous medium, and with the use of these polymers as additives or coadditives in detergents and cleaners, in the pretreatment of cotton, bleach stabilizers , as auxiliary agents in textile printing, and in the manufacture of leather, as well as for the inhibition of the hardness of water, and as a dispersing agent as well as detergents and cleaners.