SK395A3 - Graft copolymers of unsaturated monomers and sugars, process for producing the same and their use - Google Patents

Abstract

Graft polymers containing water-soluble, acid groups are disclosed with at least partial biodegrability based on sugars and monoethylenically unsaturated caraboxylic acids, sulphonic acids and/or phosphonic acids or the salts of said acids, as well as other monomers if required. A process is also disclosed for producing these graft copolymers at temperatures up to 200 C by means of radical polymerization initiators. A total mixture of 5-60 % by weight mono-, di- and olygosaccharides, their derivatives or their mixtures, and of 95-40 % by weight of a monomer mixture which contains at least one monoethylenically unsaturated carboxylic acid, at least one monoethylenically unsaturated sulphonic acid, a monoethylenically unsaturated sulphuric acid ester and/or vinyl phosphonic acid or the salts of said acids with monovalent cations, as well as if required other monomers, is polymerized. Also disclosed is the use of said graft copolymers in aqueous systems, for binding polyvalent metal ions, as water hardness inhibitors, as additives to washing and cleaning agents, as textile additives, as dispersing agents, in particular for pigments, and also as additives for paper and leather production.

Description

The present invention relates to water-soluble, acid group-containing graft copolymers which are at least partially biodegradable and based on sugars and monoethylenically unsaturated carboxylic and sulfonic acids, as well as any other monomers. The present invention further relates to their manufacture and use in aqueous systems. This includes e.g. suppression of adverse effects of water hardness, dispersing effect on dyes, use in washing solutions and dye baths, as well as auxiliary agents in the manufacture of paper and leather.

In these uses of water-soluble polymers, it is important that polyvalent metal ions are complexed, the failure of water hardness compounds is prevented, or that the dyes are dispersed in high concentration at low viscosity.

In order to increase the ecological acceptability of water-soluble polymers, many attempts have been made to produce biodegradable products. In general, the polymers that are technically used in the above applications have low degradability or cannot be degraded at all; in sewage treatment plants, large amounts of these substances bind to the mud and are thus eliminated from the aqueous system (cf. H.J. Opgenroth in Tenside Surfactants Detergents 24 (1987) 366-369, Umweltverträglichkeit von Polycarboxylaten).

Polysaccharides are perfect polymers in terms of their biodegradability, but their application technological properties are insufficient. Therefore, efforts have been made to improve the properties of polysaccharides by modifying them; for example EP 0 427 349 A2 describes the introduction of carboxyl groups by oxidation.

The calcium binding capacity of such modified polysaccharides will be improved, but will not reach the level of synthetic polycarboxylates. On the one hand, the polysaccharide acquires calcium binding capacity, on the other hand it loses part of its original biodegradability. The copolymerization by grafting of carbohydrates and unsaturated monomers containing carboxyl groups is an alternative for the synthesis of at least partially degradable water-soluble polymers. Copolymers of unsaturated carboxylic acids with monosaccharides which are capable of forming enolates in basic solutions are known from DE 37 14 732 C2? these * are partially biodegradable and their CaCO ₃ binding ability is reported to be in the range of commercial polyacrylates. Useful monosaccharides capable of forming enolates include glucose, fructose, mannose, xylose, and galactose. The manufacturing technology is expensive and complicated because the final product of this manufacturing process is the acid precipitation deposit and not the original polymer solution. Comparative Example 1 of these documents shows that the precipitated polymer is obtained not as a readily separable solid but as a fine, hardly separable sediment.

DE 38 34 237 A1 describes the use of sugars which can be produced synthetically from sucrose and fructose - palatinose and / or leucrosis - according to the polymerization process of DE 37 14 732 C2. According to the procedure of the aforementioned patents or patent application publications

J - the use of a low-cost disaccharide - sucrose - which is technically available in large quantities is explicitly excluded.

Radical initiated polymerization by grafting of non-, oligo- or polysaccharides with a combination of mono- and dicarboxylic acids which are used as detergent additives is known from DE 40 03 172 A1; these are allegedly at least partially biodegradable. In addition, the graft copolymers are attributed a comparable or even higher anti-encrusting effect in textile detergents compared to the known carbohydrate-free polymers of unsaturated mono- and dicarboxylic acids described e.g. in EP 0 025 551 B1. In addition to their problematic polymerisability, which is well known to those skilled in the art, the dicarboxylic acids listed as formulation ingredients in DE 40 03 172 A1 have a further disadvantage; this becomes apparent at the partial loss of carboxyl groups due to carbon dioxide leakage during polymerization. This development of carbon dioxide is described in the literature, for example, BRAUN in Makromol. Chemie 109 (1967) 176-193; it means that the process involves an economic loss. Moreover, this polyelectrolyte is less effective due to this partial loss of carboxyl groups. Furthermore, DE 40 03 172 A1 discloses that the use of polysaccharides involves time-consuming acid hydrolysis prior to polymerization to achieve sufficient solubility and that the polymers of the present invention often appear haze, but previous experience has shown that after a longer period of time the medium settles and an inhomogeneous product is obtained.

Japanese patent application publication no. JP-A-61-31497 describes the use of a graft polymer as a biodegradable detergent component. These graft polymers are composed of dextrin or cellulose starch polysaccharides and water-soluble water-soluble (meth) acrylic acid monomers.

Biological in the monomer range; wherein inoculated dextrin and acrylic acid polymers, wherein the dextrin content is 67 to 34% by weight, are described in particular with carboxyl groups, especially the itaconic, maleic or fumaric patent.

degradability was tested according to MITI guidelines; was 4 2-10%, m.p. j. below the content of natural material in the graft polymer. There are no data on calcium binding and hard water resistance. Although the amount of graft polymer was 20% by weight, i. was very high, the cleaning performance of a detergent containing one of said graft polymers reached only a level of comparable detergent that contained zeolite in an amount corresponding to the amount of graft polymer.

EP 0 465 287 A1 discloses a detergent composition comprising, inter alia, a graft polymer as a structural element; it is composed of synthetic polydextrose and an unsaturated water-soluble monomer. Specifically preferred are (meth) acrylic acid monomers alone or combined with maleic or itaconic acid. The examples only mention grafted polydextrose and acrylic acid polymers;

in the wash test performed compared to the zeolite, the incrustation reduction was 46%. This is much worse than the results obtained in washing tests with graft polymers according to DE 40 03 172 A1, where an inhibition of increment of up to 57% was achieved.

The graft polymers according to EP 0 465 287 A1 and JP-A-61-31497 have a substantially lower detergency effect than the compounds according to DE 40 03 172 A1. No comparable data are available to assess the calcium binding capacity or inhibition of the water hardness components of the described graft polymers. However, since both of these properties are also important in the work, it is to be assumed that the polymers according to DE 40 03 172 A1 have higher parameters.

tests can also be done in this

The object of the present invention is to prepare pure, water-soluble sugar-containing graft copolymers by a simple technique avoiding decarboxylating monomers, said copolymers having improved biodegradability and a higher efficiency compared to the present stage of development due to the property of multivalent metal ion binding? moreover, they are good inhibitors of water hardness and have dispersing properties for substances in aqueous systems.

According to the present invention, this object is achieved by a sugar copolymer and a mixture of monomers having the following composition:

A) 45-96% by weight of monoethylenically unsaturated C3-C10-monocarboxylic acids and / or their monovalent cation salts,

B) 4-55% by weight of monoethylenically unsaturated monomers containing monosulfonic acid groups, monoethylenically unsaturated sulfuric acid esters, vinylphosphonic acid and / or salts of these acids with monovalent cations,

C) 0-30% by weight of water-soluble monoethylenically unsaturated compounds modified with 2-50 moles of alkylene oxide per mole,

D) 0-45% by weight of other water-soluble radically polymerizable monomers,

(E) 0-30% by weight of other free-radically polymerizable monomers which are slightly soluble or insoluble in water, the sum of the polymerisation components A to E always giving together 100% by weight,

F) the sugar component of the graft copolymer in an amount of 5-60% by weight based on the total mixture (sum A to F).

The sugars according to the present invention are monomeric, dimeric and oligomeric compounds of the sugar units, for example natural compounds sucrose, glucose and fructose and mixtures thereof, as well as products of acid and enzymatic saccharification of polysaccharides, mixtures of mono-, dia-oligosaccharides. Sucrose, glucose, fructose and starch saccharification products are preferred, in particular because of their availability and reasonable price. In addition, reaction products obtained from saccharides such as sorbitol, mannitol, gluconic and glucuronic acid as well as alkyl glycosides, alkyl-, hydroxyalkyl- or carboxyalkyl ethers and other derivatives of said mono-, di- or oligosaccharides or mixtures thereof may be used as sugars. Oligosaccharides have an average degree of polymerization of 1.1 to 20 with a preference for 1.1 to 6. Suitable monoethylenically unsaturated C3 to C10 monocarboxylic acids listed under A) are acrylic acid, vinylacetic acid, acid

3-vinylpropionic acid, methacrylic acid, crotonic acid, dimethacrylic acid, 2-pentenoic acid, 2-hexenoic acid, their alkali or ammonium or amine salts, and their respective mixtures. Methacrylic acid, acrylic acid, vinylacetic acid are preferred, acrylic acid and methacrylic acid being particularly preferred.

Among the monomers containing sulfuric acid and the monoethylenically unsaturated sulfuric acid esters mentioned in Group B), the following are particularly preferred: vinyl, allyl and methalyl sulfonic acid and acrylaminomethylpropanesulfonic acid, styrene sulfonic acid as well as sulfuric acid esters with hydroxyethyl (meth) acrylic acid unsaturated alcohols, e.g. allyl metalylsulfate and / or salts thereof (as defined under A)).

The monomers mentioned under C) are: polyglycol ethers and / or esters of (meth) acrylic acid and (meth) allyl alcohol which may optionally be protected at one end, such as allyl alcohol etherified with 10 moles of ethylene oxide and methoxypoly (ethylene glycol) methacrylate with 20 units of ethylene oxide .

Due to their function, the monomers listed under D) have the property of increasing the molecular weight? this is achieved by a higher degree of polymerization or by branching and coupling. Therefore, suitable monomers are those that readily polymerize as well as those having two or more ethylenic double bonds acting as bifunctional cross-linking agents, or monomers with an ethylenically unsaturated double bond and another functional group. Examples include: acrylamide, allyl methacrylate and glycidyl methacrylate.

Examples of monomers according to E) include: (meth) acrylic acid alkyl and / or hydroxyalkyl ester, mono- and dialkyl maleic acid ester, as well as N-alkyl and N, N-dialkyl- (meth) acrylamide and vinyl formic esters, e.g. methyl, ethyl and butyl (meth) acrylates, corresponding to hydroxyethyl, -propyl, -, -butylmethacrylates, N-methyl, Ν-dimethyl-, N-tert-butyl N-octadecyl acrylamide, mono- and diethyl esters of maleic acid, as well as vinyl acetate and vinyl propionate provided that the copolymers prepared are water-soluble.

The sugars and monomers listed above are for illustration only and will not be construed as limiting.

The polymers of the present invention can be obtained in solution or suspension according to polymerization methods known per se. It is preferred to carry out polymerization of the monomers in aqueous solution.

Polymerization of dissociating and thermally initiated by radical polymerization initiators. Redox systems can be used to decompose compounds that produce radicals, or combinations thereof, including catalytic systems that can be initiated by radiation.

Peroxides are one of the most suitable initiators, with hydrogen peroxide and its combination with peroxosulfuric acid salts being preferred. The initiators are combined with known reducing agents such as sodium sulfite, hydrazine, heavy metal salts and others. Depending on the polymerization process, the initiator assembly may be added continuously or in batches or at changes in pH values. Molecular weights can be influenced by known methods using regulators such as mercapto compounds.

The graft copolymerization can be carried out by preparing a portion of the monomer mixture, initiating the polymerization, and then adding the monomer mixture. The sugar component is added totally to the pre-blended material or dosed together with the monomer mixture, or a portion is prepared and the other portion is dosed. The temperature during copolymerization can be varied within a wide range. This range is 0 ° C to 200 ° C. Depending on the initiators used, optimal temperatures may be between 10 ° C and 150 ° C, with a preference for the range of 20 ° C to 120 ° C. The polymerization can be carried out at the boiling point of the solvent under reduced or elevated pressure.

It can often be advantageous to carry out the polymerization under adiabatic conditions. In this case, the polymerization usually begins at low temperatures, e.g. Deň: 22 ° C. The final temperature achieved by the heat release depends on the monomers and concentration ratios used and may, for example, reach 180 ° C if the pressure is adequate.

During copolymerization, the pH can vary within wide limits. Preferably, the copolymerization is carried out at low pH values, for example those where the acrylic acid used is not or only partially neutralized and where the pH is adjusted to neutral (pH 7-8) only at the end of the polymerization, if necessary.

The graft polymers of the present invention can be produced by a continuous or non-continuous process.

The production and properties of the graft copolymers of the present invention are explained in the Examples. It is surprising that the capacity to bind polyvalent cations as compared to graft copolymers produced using maleic anhydride is considerably high. In addition, the loss of insoluble calcium and magnesium salts slows considerably when the products of the present invention are used. The dispersing efficacy of the graft copolymers of this invention is documented using talc dispersion systems, biodegradability is demonstrated by a modified MITI test and a modified Sturm test (OECD Guideline 301.)

The graft copolymers may be complexing agents; bind in water-soluble complexes. water. They are auxiliary agents and coloring solutions, with structural factors.

to be used as dispersing polyvalent metal ions They serve as hardness inhibitors in detergents and washes are particularly suitable as

The graft copolymers according to the biodegradability of the present invention show good are particularly suitable for use in textile detergents, kitchen detergents, descaling agents, water treatment agents and textile processing aids. The graft copolymers can be used in aqueous solutions, in powder or as granules.

The following table shows the usual quantities

copolymers (v in detergents and % by weight) cleaning agents. which ones the Washing powder (Textile) 3 to 30% Water softener 5 to 30% Cleaning products (eg household) 1 to 5% Dishwashing preparations (machine) 5 to 25%

vaccinated use

By way of example - only illustrative but not limiting - the following detergent and detergent compositions can be mentioned:

Washing powder alkyl benzenesulfonate, sodium salt 8% fatty alcohol ethoxylate 5% soap 3% zeolite A 25% sodium carbonate 15% sodium metasilicate 5% magnesium silicate 1% sodium perborate 20% grafted copolymers 5% sodium sulfate, water, others up to 100 %

Dishwashing detergent (machine) low suds surfactant 2% sodium metasilicate 50% sodium carbonate 5% grafted copolymers 5% sodium sulphate to 100% Washing solution low suds surfactant 10% grafted copolymers 5% isopropanol 10% cumene sulphonate 2% water up to 100%

Dishwashing (hand) paraffin sulphonate, sodium salt 20% fatty alcohol ether sulphate 5% betaine 3% grafted copolymers 2% water to 100% reverse side

5%

Multipurpose Cleaners Paraffin Sulphonate, Sodium Fatty Acid Ethoxylate Isopropanol Inoculated Copolymers Water

5%

5%

1-3% up to 100%

The polymers of the present invention can advantageously be used as auxiliary agents in the pretreatment and finishing of raw fibrous materials, fibers, textiles or textile materials. For example, in the boiling or brushing of cotton, where it binds the reinforcing agents and disperses the substances present in the cotton or impurities, avoiding their re-depositing and promoting the effect of the surfactants. The polymers of the present invention are used as stabilizers in bleaching with hydrogen peroxide and prevent the deposition of silicates by the additional use of stabilizing silicates.

The polymers of the present invention can also be used as adjuvants in continuous and discontinuous washing and coloring solutions while removing unbound dye and achieving good dye, water and abrasion or rub resistance. In the case of polyester fibers, the dispersing effect of the polymers has the effect of separating the dissolving oligomeric components of the polyester which interfere with the dyeing process.

The polymers of the present invention are suitable auxiliaries for dyeing natural and / or synthetic fibers or textiles. For example, the dyeing of cellulosic fibers promotes the solubility of reactive and direct dyes and achieves a more even coating of the fibers with the dye, especially when large amounts of salt are present in the solution.

In vat dyes, they can advantageously be used as a dye transfer agent or as a dispersant in the dye bath. In sulfur dyeing they promote dye dispersion and prevent browning. In dyeing synthetic fibers, the polymers of the present invention prevent agglomerates from dispersed dyes, thereby avoiding cone deposition.

replacement side of the dye into the washing solution by polymers removal of unbound dyes during the investigation For this reason, the products of the present effective replacement of polyphosphates in the final dyed naphthol dyes; when dyes are washed out, alginate failure is prevented

The graft polymers of the present invention can be used as an auxiliary agent in fabric printing, especially in the elution of reactive dyes and the colors of natural and / or synthetic fibers or textiles. Unbound dye components bind to them and new deposition is greatly reduced. Due to the increased diffusion they achieve optimum water and energy, the present invention is represented by the treatment of reactive calcium carbonate products.

The dispersing and complexing effect of the polymers of the present invention proceeds without restoring the mobility of the light metal compounds both from chromophores of dyes (reactive dyes and metal complex dyes) and from water-insoluble deposits of natural or industrial origin.

The amounts required in practice can be reduced, three to four times as necessary, when conventional auxiliary agents such as polyacrylates are used.

The polymers of the present invention can be used in combination with surfactants, especially anionic non-neutralized form (such as acid complexing organic acids such as lactic acid, gluconic acid and surfactants, especially anionic surfactants).

Such combinations are preferably used, for example, as a substitute for conventional multi-stage treatment, which is carried out in separate baths, for example, to treat heavily dyed cotton or linters (short fibers remaining on cotton seeds after first egrenation) with acid extraction stages, chlorite bleaching, cooking and bleaching H ₂ O ₂ ; this is done in a manner where the preparation takes place in only one adjustable bath with the addition of the polymers of the present invention.

This method of the present invention can also be applied to the active agents (in treatment) in combination with citric acid, and phosphonic acid substitute continuous processes. These methods prevent the occurrence of undesirable organic halogenated environmental damage.

These polymers are suitable from fibers which are sensitive to the compounds of the corresponding fat removal additives to the water hardness and are bonded to natural and / or synthetic fibers or textiles.

In leather processing, the polymers of the present invention provide enhanced chromium binding to the skin during chrome dyeing, and chromium dyed contributes to the skin fullness and softness properties.

Due to their properties of suspension and complexation of heavy metals, while not restoring mobility, the polymers of the present invention can also be advantageously used as auxiliary agents in paper making, for example in the preparation of pigment and filler suspensions such as kaolin, calcium carbonate, satin white, talc, oxide titanium dioxide, alumina and barium sulphate, as well as in the preparation of coatings with a high solids content and high storage stability.

The polymers of the present invention may be used in combination with other adjuvants.

The products have a high ecological acceptability because the polymers of the present invention have a high efficiency resulting in a low concentration used and due to their good biodegradability.

The polymerization reactions illustrated in the following examples and comparative examples were carried out in a 2 liter reaction flask equipped with a stirrer, reflux condenser, thermometer, and dosing mechanism for liquid and gaseous substances.

Examples 1-7

A mixture of acrylic acid, sugar, sodium metalylsulfonate and another comonomer and water was partially neutralized with 50% sodium hydroxide solution in the reactor, cooled to 25 ° C and 8.8 g mercaptoethanol, 0.02 ferrous sulfate in 10.0 g water and 3 g 35 were added. % hydrogen peroxide. When the temperature in the reactor rises above 75 ° C due to the initiating polymerization reaction, it is cooled to 75 ° C after reaching the maximum temperature. When the temperature remains below 75 ° C, it is heated to 75 ° C when the maximum temperature is reached. Thereafter, 2 g of hydroxylammonium chloride in 15.7 g of water and 14.3 g of 35% hydrogen peroxide are added to the reactor and waiting for the temperature to rise again. Upon completion of the exothermic reaction, the mixture was heated to 95 ° C and maintained at this temperature for 2 hours followed by cooling and meutralization with a 50% hydroxide solution at 40-45 ° C. The polymers are brown and colorless. The amounts used and indications for the polymers are shown in Table 1.

Example 8

The polymerization process corresponds to that of Examples 1 to 7, except that partial neutralization is initially omitted and the polymerization is carried out in an acidic medium.

Examples 9 to 11

The polymerization process corresponds to that of Examples 1 to 8, except that 4.4 g of mercaptoethanol is used.

The results are shown in Table 1.

Table 1

Example Acid a sugar - Quantity in g - acrylic component metalyl konomonomer solution water viscosity Contents sulfonate hydroxide (MPa.s) solid sodium sodium substances (t) You're welcome. the end

1 140 108.9 sucrose 72.6 36 +114.7 474 20 39.1 2 112 145.2 sucrose 72.6 28.8 +81 506 31 38.3 3 212 150 sucrose - 150 AMPS * 54.6 +173.9 205 1200 51.1 4 126 108.9 sucrose 90.8 32.4 +103.3 485 34 37.8 5 168 72.6 sucrose 72.6 43.2 +137.7 452 72 39.5 6 238 36.3 sucrose 18.1 61.2 +195 397 200 39.4 7 154 108.9 sucrose 54.5 39.6 126.2 463 40 37.9 8 212 150 sucrose 75 - +228.4 288 780 52.0 9 140 109 sucrose 54.5 18.3 MPEG-36 1000 HA ** +114.7 441 56 37.7 10 140 190 sucrose 36.3 36.3 AAEO- 36 20 * " +114.7 478 68 37.4 11 140 109 sucrose 36.3 36.3 AAEO- 36 +114.7 478 48 37.9

10 "" * = 50S acrylamidopropanesulfonic acid sodium salt solution "= methoxy (polyethylene glycol) methacrylate, molar mass 1068 = allyl alcohol ethoxylate with 20 moles of ethylene oxide" "= allyl alcohol ethoxylate with 10 moles of ethylene oxide

Example 12

224 g of acrylic acid are mixed with 381.6 g of water in a polymerization reactor and partially neutralized with 64 g of 45% sodium hydroxide solution. To this solution is added 36.3 g of sucrose and 36.3 g of sodium metalylsulfonate. Then 8.8 g of mercaptoethanol, 0.02 g of ferrous sulfate in 10.0 g of water and 3 g of 35% hydrogen peroxide are added. The temperature rises from 25 ° C to 101 ° C and drops again. At 75 ° C, 2 g of hydroxylammonium chloride in 15 g of water and 14.3 g of 5% hydrogen peroxide are added, causing the temperature to rise to 79 ° C. The temperature is raised to 95 ° C by heating and maintained at this temperature for 2 hours. Then 15 g of 35% hydrogen peroxide are added, the temperature is lowered to 70 ° C and the mixture is neutralized with 204 g of 45% sodium hydroxide solution and the polymerization is allowed to continue for 30 minutes at 70 ° C. The prepared polymer is light brown and transparent, has a dry substance content of 41.1% and a viscosity of 80 mPa.s and a pH of 6.6. The number and weight average molecular weights are as follows: Mn = 1412 and Mw = 4939. The residual monomer content for acrylic acid is 0.006% and for sodium metalylsulfonate 0.143%.

Example 13

82.2 g of acrylic acid is diluted with 414.8 g of water and mixed with 21.1 g of sodium hydroxide solution (50%), 58.1 g of sodium methallyl sulfonate, 116.2 g of sucrose and 205.4 g of acrylamide solution (40% aqueous). solution). After adding 8.8 g of mercaptoethanol, 0.02 g of ferrous sulfate in 10 g of water and 3 g of 35% hydrogen peroxide, the temperature rises from 25 ° C to 70 ° C, when 2 g of hydroxylammonium chloride in 15 g of water and 3 g 35% hydrogen peroxide. As a result, the temperature rises to 79 ° C and is increased to 95 ° C by the bath and is thus maintained for 2 hours. It is then cooled to 45 ° C and neutralized

67.3 g of 50% sodium hydroxide solution. The polymer is dark brown and transparent, the solids content is 36.8%, the viscosity is of the order of 35 mPa.s and the pH value is 7.00.

Example 14

192.8 g of acrylic acid are mixed with 272.6 g of water, 55.1 g of 45% sodium hydroxide solution, 10 g of sodium metalylsulfonate and 150 g of sucrose. At 25 ° C 8.8 g of mercaptoethanol, 0.02 g of ferrous sulfate in 10 g of water and 3 g of 35% hydrogen peroxide are added. The temperature rises again to 91 ° C and drops again. At 72 ° C, 2 g of hydroxylammonium chloride in 15 g of water and 14.3 g of 35 hydrogen peroxide are added, after which the temperature rises to 93 ° C. 2 g of hydroxylammonium chloride in 15 g of water and 14.3 g of 35 hydrogen peroxide are again added and the temperature is maintained at 95 DEG C. for 2 hours. The polymer is transparent and has a dark brown color, a pH of 6.3, a viscosity of about 530 mPa · s and a solids content of about 51.2%. The number and weight average molecular weights were Mn = 841 and Mw = 2554. The residual acrylic acid content was 0.002% and the sodium metalylsulfonate content 0.77%.

Example 15

30% by weight of a mixture consisting of 212.1 g acrylic acid, 150 g sucrose, 75 g sodium methallyl sulfonate, 287.7 g water and 54.6 g 50% sodium hydroxide are charged to the reactor and 2.6 at 21 ° C are added. g of mercaptoethanol, 0.9 g of 5% hydrogen peroxide and 0.02 g of ferrous sulphate in 8.6 g of water, the temperature rising to 86 ° C. 6.2 g of mercaptoethanol and 0.02 g of iron (II) sulfate in 8.6 g of water are then added and the remainder of the monomer mixture together with a solution of 2.1 g of hydrogen peroxide in 1.4 g of water are simultaneously metered over an hour. The temperature is maintained at 85 ° C. At the end of dosing, 14.3 g of 35% hydrogen peroxide are added. The temperature rises to 97 ° C and drops again. When the temperature reaches 85 ° C, 2 g of hydroxylammonium chloride in 8.5 g of water are added and the temperature is maintained for 2 hours. It is then cooled to 40 ° C and neutralized with 173.8 g of 50% sodium hydroxide solution. The polymer is dark brown and transparent, the solids content is 52.8%, the pH value

6.7 and a viscosity of 1040 mPa.s. The number and weight average molecular weights were Mn = 1755 and Mw = 6773. The residual acrylic acid content was 0.01% and the sodium methalylsulfonate content 0.32%.

Example 16

212.1 g of acrylic acid are mixed with 281.3 g of water, 54.6 g of 50% sodium hydroxide solution, 75 g of sodium metalylsulfonate and 150 g of sucrose; at 25 ° C, 8.8 g of mercaptoethanol, 0.02 g of ferrous sulfate in 10 g of water and 3 g of 35% hydrogen peroxide are added. The temperature rises to 101 ° C and then drops again. At 80 ° C, 2 g of hydroxylammonium chloride in 8.6 g of water and 5 g of sodium persulfate in 15.0 g of water are added and the temperature is maintained at 85 ° C for 70 minutes. After cooling to 40 ° C, the mixture was neutralized using 173.8 g of 50% sodium hydroxide solution. The polymer is transparent and yellow, has a solids content of 51.5% and a viscosity of 360 mPas and a pH of 6.5.

Example 17

212.1 g of acrylic acid are mixed with 2.5 g of trialylamine, 281.3 g of water, 54.6 g of 50% sodium hydroxide solution, 75 g of sodium methallyl sulfonate and 150 g of sucrose. 0.02 g of ferrous sulfate in 10 g of water and 3 g of 35% hydrogen peroxide are added to the mixture at 20 ° C. With gentle heating, the temperature rises to 102 ° C for 90 minutes. It is then allowed to cool to 75 ° C, 2 g of hydroxylammonium chloride in 15 g of water and 14.3 g of 35% hydrogen peroxide are added and stirring is continued for 1 hour at 95%. It is then cooled to 40 DEG C. and 174 g of 50% sodium hydroxide solution are neutralized. The polymer is transparent and brown, with a solids content of 52.3%, a viscosity of 1900 mPa.s and a pH of 7.6. The number and weight average molecular weights were Mn = 2558 and Mw = 8467.

Example 18

74.7 g of acrylic acid, 26.4 g of sodium metalylsulfonate, 150 g of sucrose, 186.6 g of water and 43.4 g of sodium hydroxide are dissolved together, placed in a reactor and heated to boiling. A solution of 137.4 g of acrylic acid, 48.6 g of sodium methanesulphonate and 50 g of water was added in portions over 5 hours, and 80 g of 30% hydrogen peroxide and 96 g of 25% aqueous sodium persulfate solution were added over 6 hours. This is followed by stirring for 1 hour; cooling to 40 ° C and neutralizing 166.9 g of 50% sodium hydroxide solution. The polymer is transparent and colorless, has a solids content of 52% and a viscosity of 820 mPa.s. The residual monomer content is 0.002% for acrylic acid and 0.025 for sodium methalylsulfonate. The number and weight average molecular weights were Mn = 2014 and Mw = 5135.

Example 19

190.8 g of acrylic acid, 261.0 g of water, 49.0 g of 50% sodium hydroxide solution, 150 g of sucrose, 75 g of sodium metalylsulfonate and 21.2 g of vinyl acetate are dissolved together and charged to the reactor. After adding 8.8 g of mercaptoethanol, 0.02 g of ferrous sulfate in 10 g of water and 3 g of 35% hydrogen peroxide, the temperature rises from 23 ° C to 88 ° C and drops again to 75 ° C when 2 g of hydroxylammonium chloride are added. in 15 g of water and 14.3 g of 35% hydrogen peroxide. For a short time the temperature rises to 90 ° C and is maintained at this value for 1 hour using a bath. A water separator is fitted to distill off unreacted vinyl acetate. Within one hour, 5 g of vinyl acetate and 31.7 g of water were separated, increasing the temperature in the reactor to 99 ° C. It is then cooled and neutralized with 50% sodium hydroxide solution. The polymer is transparent and has a dark brown color, a solids content of 51%.

Comparative Example 1 (according to DE 37 14 732 C2, Example 2)

108 g of acrylic acid are neutralized with 300 g of 20% sodium hydroxide solution. Dissolve 91 g of glucose in 100 g of water and mix with 49 g of a 35% H ₂ O _{2 solution} . 100 g of water is heated to 85 ° C in a reaction vessel and acrylic acid and glucose solution are added over 90 minutes while maintaining the pH at 9.0. 10 minutes after the addition was complete, the temperature in the reaction flask suddenly rose to 103 ° C and the polymer was decolorized in yellow. The mixture was then cooled. The polymer solution has a solids content of 30.6% and a viscosity of 220 mPa.s. By adding hydrochloric acid, the polymer can precipitate in the form of a lubricating failure.

Comparative Example 2 (according to DE 40 03 172 A1, Example 21)

243 g of water, 160 g of sucrose, 47.9 g of maleic anhydride, 0.57 g of phosphoric acid and 2 g of sodium bisulfite are added to the reaction flask and stirred for 1 hour at 80 ° C under a stream of nitrogen. Subsequently, 70.5 g of a 50% sodium hydroxide solution are slowly added, and a solution of 133.6 g of acrylic acid in 141.9 g of water is added in portions over 5 hours at 80 ° C and periodically over 6 hours solutions of 8 are added. 1 g of 35% hydrogen peroxide and 2.85 sodium sulfate in 40 g of water. The mixture is then subjected to a final heat treatment for 2 hours. The polymer solution has a solids content of 37.7% and a viscosity of 155 mPa.s.

Comparative Example 3 (according to DE 40 03 172 A1, Example 25)

290 g of maltodextrin MD 14 (dextrose equivalent value 14, Avebe), 470 g of water, 4.2 ml of a 0.1% aqueous ammonium sulfate solution, 101.4 g of maleic anhydride and 74.5 g of sodium hydroxide are placed in a reaction flask and heated. to the boil. After boiling, a mixture of 120 g of acrylic acid and 123.7 g of a 50% aqueous solution of acrylamidomethylpropanesulfonic acid sodium salt was added in portions over a period of 5 hours, and 80 g of 30% hydrogen peroxide and 24 g of sodium persulfate in 72 was added over 6 hours. g of water, maintaining the temperature such that the mixture boils. After addition of the last initiator batch, the mixture is subjected to a final heat treatment for 1 hour. 155 g of 50% sodium hydroxide solution are then neutralized. A cloudy brown solution is obtained with a solids content of 45.2% and a viscosity of 560 mPa.s. Within 14 days a blackout occurred.

Comparative Example 4

108.9 g sucrose, 185 g water, 77 g maleic anhydride, 2.2 mg

I of ammonium ferric sulfate and 112.8 g of 50% sodium hydroxide solution are placed in the reactor and heated to boiling. After boiling, a solution of 77 g of acrylic acid, 54.4 g of sodium methallyl sulfonate and 94 g of water is added over 4 hours, and then a solution of 34 g of 35% hydrogen peroxide, 12 g of sodium persulfate and 66 g of water is added over 5 hours. This is followed by stirring at reflux for one hour and neutralization with 93.6 g of 50% sodium hydroxide solution. The brown polymer solution is transparent, has a viscosity of 74 mPa · s and a solids content of 43.8%. The development of carbon dioxide can be observed throughout the polymerization reaction.

Comparative Example 4 was carried out according to DE 40 03 172 A1 using maleic anhydride as monomer; shows the loss of carboxyl groups in the development of CO ₂ in the calcium binding capacity (Table 4) of the present invention of Comparative Example 4 differs and a dramatic decrease in comparison with polymer 7. The monomer composition of Example 7 is merely the fact that maleic anhydride.

acrylic acid was replaced

Comparative Example 5

154 g of acrylic acid, 444 g of water, 54.5 g of sodium methysulphonate, 113.7 g of maltodextrin (dextrose equivalent value of 20) and 39.6 g of 50% sodium hydroxide solution are dissolved in the reactor and 4, 4 g mercaptoethanol, 0.02 g iron (II) sulfate in 8.6 g water and 3 g 35% hydrogen peroxide in 1.4 g water. The temperature rises to 62 ° C. Then 2 g of hydroxylammonium chloride in 8.6 g of water and 14.3 g of 35% hydrogen peroxide in 7 g of water are added. The temperature rises again and reaches a maximum at 75 ° C. The temperature is then raised to 95 ° C with an external bath and maintained at that temperature for 2 hours. The mixture was then cooled to 30 ° C, neutralized with 126.2 g of 50% sodium hydroxide solution and treated

13.7 g of water to a solids content of 36.5%. The polymer is turbid, has a brown color viscosity of 90 mPa.s. The turbidity settles in the form of sediment within a few days.

Comparative Example 5 was carried out according to Example 7, but the sugar component was replaced by a starch derivative (maltodextrin). This shows that the use of higher molecular polysaccharides often results in cloudy and non-homogeneous polymers.

Determination of hard water resistance

A certain amount of the 10% seeded copolymer solution is added to the test water at 33.6 ° dH [= German water hardness scale] (pure calcium hardness), boiled on a heating plate for 5 minutes and then assessed for transparency, opalescence and turbidity. When varying the amount of graft copolymer, the concentration of gram product (solids content) per liter of hard water is determined, i. concentration at which a clear solution appears for the first time after previous turbidity.

The results clearly demonstrate that the polymers of the present invention can provide effective prevention against boiler scale or similar deposits or failure of hard water components.

Table 2

Product

Example

Clear hard water resistance at (g solid / 1)

Comparative example 1 Comparative example 2

1.5 2.0 0.5 2.0> 1.0

2.5> 3.0

3.0

Dispersion tests

To demonstrate the dispersing effect of the graft copolymers of the present invention on pigments, talc (Finntalc CIO, from OMYA) was blended into aqueous solutions of graft copolymers at pH 12.0 up to a pigment content of 65%, viscosity was measured immediately and after 7 days, and miscibility (1 to> 6) was determined. A combination of POLYSALZ ^R- S / LUMITEN ^R -PT (BASF AG) was used as a replacement standard representing the most advanced agent in the field. The addition of dispersing agent was up to 0.2% / abs. of dry pigment and, in the case of POLYSALZ ^R- S / LUMITEN ^R -PT, up to 0.15 / 1% in abs. dry pigment.

Table 3

Suspension viscosity (mPa.s, Brookf., 100 rpm) Miscibility 1: Mon 14 d. 6: very good very bad time storage dispersant immediately Mon 7 d. Example 1 262 261 280 3-4 Example 3 lumiten ^r pt 290 455 3 + polysalz ^r p 280 340 358 3

Determination of calcium binding capacity

The calcium binding capacity is determined according to the so-called Hampshire test, where the polymer is titrated with a calcium acetate solution in the presence of carbonate ions. The final titration value is expressed in mg CaCO 2 / g polymer.

Procedure: Dissolve 1 g of complexing agent in 50 ml of distilled water, neutralize with sodium hydroxide solution and add 10 ml of 2% sodium carbonate solution; make up to 100 ml and adjust to pH 11.0. Titrate with 0,25 ml of calcium acetate solution until a permanent turbidity or failure occurs. The stage immediately before turbidity is recognized by light opalescence; the transition is either narrow or wide depending on the complexing agent. The complexing effect of some of the polymers of the present invention is so high that, apart from mild opalescence, no haze is observed.

Table 4

Product Example no.

Hampshire Calcium Binding Capacity (mg CaCO ₃ / g polymer)

9 easy opalescence, easy opalescence,

18

Comparative dia. 1 Comparative dia. 2 Comparative diam. 4

1898

990 no turbidity 2104 2148 1642 2061 no turbidity 1931 2972 1169> 3000 2216 1450 1490 2172 299 697 497

The polymers of the present invention exhibit very high calcium binding properties. If additionally maleic anhydride (Comparative Examples 2 and 4) is used, or in the absence of monomers containing sulfuric acid groups (Comparative Example 1), polymers with reduced calcium binding capacity are obtained.

Biodegradability

Biodegradability can be determined by several methods. The so-called Zahn Wellens test, for example, determines the reduction of carbon in a test medium containing a sewage sludge. Decreased carbon content can occur either by biodegradation or by adsorption to sludge, a clear interpretation of the results is not possible.

Therefore, it has been used to assess biodegradability

I modified MITI test (OECD Test Guideline 301 for Chemicals); this test measures the oxygen consumption during degradation. Assay errors due to adsorption to sludge do not occur. In said MITI-test, the grafted polymer of Example 7 showed a biodegradation of 78.5% B.O.D./C.O.D. after 28 days. This result represents good biodegradability.

Table 5

Time (Days) Biodegradability (% B.O.D. / C.O.D.) 0 0 7 0 14 46.5 21 61.0 28 78.5

STURM test according to EC directive 84-449-EWG C5 and OECD directive no. 301 B was used as another degradation test. The biodegradation of the polymer of Example 20 was monitored for carbon dioxide evolution over 28 days and was 89%.

Time (days) Biodegradability (% B.0.D. / C.0.D.) 30 min 1 3 18 7 34 12 51 18 76 21 77 26 91 28 89

Example 20

Example 9 is repeated except 36.3 g of methoxypolyethylene glycol and 36.3 g of sodium methalylsulfonate are used.

I

The polymer has a solids content of 36.3%, a pH of 6.3 and a viscosity of 80 mPa.s. The number and weight average molecular weights were determined: Mn = 2009 and Mw = 7170.

Example 21

8.83 g mercaptoethanol, in 10 g water) and 3 g 35% in 5 g water) are added to

0.02 ferrous sulphate (dissolved hydrogen peroxide solution (dissolved solution 154 g acrylic acid, 39.6 g 50% sodium hydroxide solution, 108.9 g sodium sulfatoethyl methacrylate (50% aqueous solution), 136.1 g glucose in 372 g water) at 25 [deg.] C. The temperature rises to 80 [deg.] C. over 9 minutes, when 2 g of hydroxylamine hydrochloride (dissolved in 10 g of water) and 14.3 g of 35% hydrogen peroxide (dissolved in 10 g of water) are added. heated to 95 ° C and held at this temperature for 2 hours, after cooling 126.2 g of sodium hydroxide solution was neutralized The polymer had a solids content of 36.1%, a pH of 5.5 and the following average molecular weight values: Mn = 1684 and Mw = 6800.

Example 22

Example 3 is repeated except that an equivalent amount of vinylphosphonic acid is used instead of AMPS. During the initial phase, the polymerization process slows down a bit, but becomes briefly exothermic again after a brief gentle heating. The polymer has a dry component content of 52.0% and a viscosity of 960 mPa.s; the pH is 5.4.

Example 23

According to the experimental procedure of Examples 1-7, a polymer is prepared with the following monomer components:

Initial mixture: 61.6 g acrylic acid, 43.6 g hydroxyethyl glycoside, 21.8 g sodium methallyl sulfonate, 170.5 g water and 15.8 g 50% sodium hydroxide solution.

Initiation: 3.5 g mercaptoethanol, 8 mg ferrous sulfate dissolved in 8 g water, 1.2 g hydrogen peroxide (35%) and 0.8 g hydroxylamine hydrochloride dissolved in 8 g water and 5.7 g hydrogen peroxide (35%) ) dissolved in 7 g of water.

Neutralization: 50.5 g sodium hydroxide solution (50%).

The polymer has a solids content of 34.5%, a pH of 7.0 and a viscosity

37.5 mPa.s. The Hampshire calcium binding capacity is 1369 mg CaCO ₃ / g polymer solids.

Example 24

Example 3 was repeated, but instead of AMPS monomer was used

187.5 g of a 40% solution of sodium allyliminodioic acid. The polymer had a solids content of 53.0% and a viscosity of 1210 mPa.s.

- Hard water resistance is 2.0 liter. g of polymer solid component per • Example 25 192.8 Acrylic acid is diluted 276.7 g of water and mixed with 49.6 g sodium hydroxide solution (50%), 150.0 g sucrose, 75

g of sodium metalylsulfonate and 25 g of methoxypolyethylene glycol methacrylate (17 moles EO). After the addition of 20 mg of ferrous sulfate dissolved in 10 g of water and 4.4 g of mercaptoethanol, polymerization is started by adding 3.0 g of 35% hydrogen peroxide dissolved in 10 g of water. After reaching a maximum temperature of 87 ° C, the solution is added

4.5 g sodium persulfate in 40 g water followed by stirring at 95 ° C for 2 hours. After cooling, the mixture was neutralized with 158.0 g of 50% sodium hydroxide solution. The polymer has a solids content of 50.0% and a molecular weight Mw = 6x10 ³ and Μη = 1.8x10 ³ , and a hard water resistance of 1.5 g polymer solids / l.

According to Example 25, a polymer was prepared in which the content of sodium metalylsulfonate and methoxyethylene glycol (17 moles EO) was 50 g each. The product had a solids content of 50% and showed no deposits on turbidimetric titration performed to determine the calcium binding capacity. The hard water resistance was of the order of 1.5 g polymer solids / l.

Example 26

Washing of dyed material

The use of the polymers of the present invention is described with reference to discontinuous washing of a cotton fabric subjected to reactive dyeing.

First, the coloring solution is drained, followed by:

1. Rinse with flow at 60 ° C for 10 min

2. Rinse in fresh bath at 90 ° C for 10 min

3. standing with 1 g / l of the polymer of Example 9 at 90-95 ° C for 10 min. Rinsing at 45 ° C for 15 min.

The cotton fabric is intense in color, lint-free and has good wash resistance.

The time periods, temperatures and procedures shown are illustrative only. The polymers of the present invention may also be used under other washing conditions.

Example 27

The behavior of dispersing agents in highly alkaline solution

Test solutions (500 mL) of water with 25 ° dH, 10 g / l NaOH and the polymer of the present invention are heated to boiling, held at this temperature for 15 minutes and then cooled. The volume loss of the solution is compensated by the addition of water (20 ° dH).

Table 6 indicates the appearance of the solutions depending on the amount used and compared to the commercial products I, II and III:

Table 6

Quantity used 0.5 g / l 1 g / i 2 g / l 3 g / l Product product I flocculate flocculate flocculate limpid product II flocculate flocculate opál.-clear limpid product III opál.-hazy limpid limpid limpid polymer according to pr. 25 opál.-hazy limpid opál.-clear limpid

Clear solutions are obtained using amounts from:

g / l at 1 g / l at II g / l at III g / l of the polymer of Example 25.

Example 28

The raw cotton threads are boiled with 5 ml of acetic acid at a liquor ratio of 1:10 for 30 minutes. Then 200 ml of the solution is cooled to 60 ° C and the following is added:

0.5 g / l, 1.0 g / l and 2 g / l of the polymer of Example 25

0.05 g / L indantrene blue BC Coll

20.0 ml / l NaOH, 50% a

5.0 g / l bisulfite, equ.

After standing for 15 minutes (at 60 ° C), the liquor was aspirated through a Blauband-Filter.

The polymers have a good dispersing effect; at the concentrations used, they prevent the flocculation failure.

alternate side

Example 29

At a leach ratio of 1:20 and a temperature of 70 ° C to 80 ° C, the dark colored PES was treated with 1 g / l of the polymer of Example 25 and 1 g / l of SOLOPOL ^R DP (fatty amine ethoxylate, trade mark Chemische Fabrík Stockhausen GmbH). , Krefeld) for 20 minutes; followed by hot and cold rinsing.

Oligomers, color and fiber dust were removed from the fibers.

Example 30 g of the polymer of Example 16 is dissolved in distilled water in a 500 ml volumetric flask and the flask is filled to the mark. Pipette 10 ml of the resulting solution into a 150 ml beaker and dilute with 80 ml of distilled water.

Different amounts of FeCl 3 solution containing 48.41 FeCl ₃ .6H ₂ O per liter in dissolved form were added to each batch. The desired pH was then adjusted with 0.1 N NaOH or 0.1 N HCl. The solution was transferred to a 250 mL round bottom flask and refluxed for 1 hour.

After cooling to room temperature, an assessment is made.

In order to determine the iron-binding capacity, a dose of a concentration series that does not yet show turbidity or failures is used, the next dose already showing turbidity or failure.

The calculation is made in mg Fe ³⁺ / 1 g solid product.

PH iron binding capacity mg Fe ³⁺ / g solid component 7 600 9 800 11 350

alternate side

Example 32

Bleaching of a 100% cotton linter with a degree of whiteness of 29.5 (according to Elrepho) was carried out in a 1: 20 liquor bath with the following steps:

Step 1 Liquid treatment with 1 mL / 1 HCl, equ. (37%) ml / 1 combination consisting of:

42.0 parts of the polymer of the present invention according to Example 25 in a final acid treatment

10.0 parts of lactic acid 25.0 parts of gluconic acid 4.0 parts of phosphonic acid

14.0 parts of C12-C18 fatty alcohol polyglycol sulphate parts by foaming of an EO-PO blocking polymer for 30 minutes at 25 ° C.

Step 2 A) Treatment of the liquor with ml / l NaOH, 50% g / l Lavoral ^R S313 (commercial product Chemische Fabrik Stockhausen GmbH) for 45 minutes at 95 ° C

B) Treatment with 10 ml / l NaOH, 50% g / l of the combination of step 1 for 45 minutes at 95 ° C

C) Treatment with 10 ml / l NaOH, 50% g / l of the polymer of the invention of Example 25 for 45 minutes at 95 ° C

Step 3

Caustic treatment from ml / l of the combination according to step 1 ml / l of hydrogen peroxide, 35% for 45 minutes at 95 ° C

The hydrogen peroxide was previously diluted in a solution of the combination of step 1 and an amount of water and added slowly hot.

The liquor is drained and the material is hot rinsed at 80 ° C with the addition of 2 ml / L of the polymer of Example 25.

Three samples of bleached material have a degree of whiteness of 68.7 / 69.8 / 69.7.

Example 33

Leather processing

The suitability of the polymers of the present invention in leather processing is shown in the following with reference to chrome dyeing of the skin and dyeing of the upper skin. In chrome dyeing, the skin is treated in chromium salt solutions to incorporate chromium into the collagen skin structure. From the aqueous solution, as much chromium as possible should enter the skin. For this application, the polymer of Example 7 according to the present invention was used and showed a good result - the chromium content was greatly increased.

Table 7

Chromium content in residual Chromium oxide content in the skin humidity before AFTER before after application polymer (%) use of polymer (g / l) 3.51 0.56 2.3 3.3

The following criteria should be used when coloring the upper skin: softness, fiber tightness, skin color and fullness. In comparison with a commercial coloring agent based on acrylamide / acrylic acid, said polymer was tested according to the invention.

of Example 7 with the following result:

Table 8

The polymer of Example 7 commercial polymer softness 2 3 Tightness of the fiber 3 2 Leather color very clear clear Solidity (mm) 1.8 - 1.9 1.9 - 2.0

* Rating scale: 1-6, with 1 being the best replacement side

Claims (20)

PATENT Seeded copolymers and oligosaccharides as well as their mannitol, gluconic acid monosaccharides, disaccharides of reaction products such as sorbitol, and glucuronic acid, as well as alkyl glycosides, alkyl-, hydroxyalkyl- or carboxyalkyl ethers and monomer mixture obtainable by free radical graft copolymerization mixtures containing A) 36.95-96% by weight of at least one monoethylenically unsaturated C3-C10 monocarboxylic acid and / or its monovalent cation salt or mixtures of C3-C10 monocarboxylic acids and / or their monovalent cation salts, B) 4-55% by weight of at least one monoethylenically unsaturated, sulfone-containing monomer, one monoethylenically unsaturated sulfuric acid ester and / or vinylphosphonic acid and / or its monovalent cation salts, C) 0-30% by weight of at least one water-soluble, monoethylenically unsaturated (meth) allyl alcohol polyalkylene glycol ether or (meth) acrylic acid polyethylene glycol ester, which may optionally be protected at one end, and 2-50 moles of alkylene oxide units per mole of methacrylic acid or (meth) allyl alcohol, D) 0-45% by weight of at least one other water-soluble radically polymerizable compound that increases the molecular weight due to an increased degree of polymerization such as acrylamide, or which comprises at least two ethylenically unsaturated double bonds or one spare side of an ethylenically unsaturated double bond along with another a cross-linking functional group and thus increases the molecular weight, E) 0-30% by weight of radically polymerizable alkyl and / or hydroxyalkyl esters of (meth) acrylic acid, monoalkyl esters and dialkyl esters. maleic monomers, as well as N-alkyl- and N, N'-alkyl (meth) acrylamides and vinylcarboxylic acid esters, which are sparingly soluble or insoluble in water, the sum of A to E giving 100% by weight, in the presence of mono-, di- and oligosaccharides, their reaction products such as sorbitol, mannitol, gluconic acid, glucuronic acid as well as alkyl glycosides, alkyl, hydroxyalkyl or carboxyalkyl ethers or mixtures thereof, wherein the content of said carbohydrate components in the mixture is 5-60% by weight. Seeded copolymers according to claim 1, characterized in that they comprise as monomers A acrylic acid and / or methacrylic acid, their alkali / ammonium and / or amine salts. Seeded copolymers according to claim 1, characterized in that they comprise as monomers B allylsulfonic acid, metalylsulfonic acid, acrylamidomethylpropanesulfonic acid, vinylsulfonic acid, sulfatoethyl (meth) acrylate and vinylphosphonic acid and / or salts of said monovalent cations. The graft copolymers according to claim 1, characterized in that they comprise allyl alcohol or unsaturated carboxylic acid esters such as acrylic acid or methacrylic acid, the alcohol component of which has been modified with alkylene oxide as water-soluble monoethylenically unsaturated alkylene oxide modified compounds. The graft copolymers according to claim 1, characterized in that they comprise, as a replacement side, monomer D, molecular weight-increasing monomers and those having multiple monoethylenically unsaturated double bonds or those having an ethylenically unsaturated double bond and another functional cross-linking group. 6. The graft copolymer of claim 1 characterized in that the monomer E as acrylamide, alkyl and / or hydroxyalkyl esters of (meth) acrylate, mono- and dialkyl esters of maleic _acid, and N-alkyl and N, N-dialkyl ( meth) acrylamide and esters of vinyl carboxylic acid. Process for preparing graft copolymers according to claims 1-6 from mono-, di- and oligo-saccharides, their reaction products, their derivatives or mixtures thereof and monoethylenically unsaturated monomers in solution or suspension at temperatures up to 200 ° C by means of radical polymerization initiators, characterized by wherein a total mixture of 5-60% by weight of mono-, dia-oligosaccharides, their reaction products and derivatives or mixtures thereof and 95-40% by weight of a monomer mixture consisting of? A) 45-96% by weight of at least one monoethylenically In an unsaturated C3-C10 monocarboxylic acid or a salt thereof, with monovalent cations, B) 4-55% by weight of at least one monoethylenically unsaturated monomer containing sulphonic groups, one monoethylenically unsaturated sulfuric acid ester and / or vinylphosphonic acid and / or salts thereof with monovalent cations, C) 0-30% by weight of at least one water-soluble, monoethylenically unsaturated compound modified with 2-50 moles of alkylene oxide per mole, D) 0-45% by weight of at least one other water-soluble, radically polymerizable monomer, back side (E) 0-30% by weight of other radically polymerizable monomers, which are poorly soluble or insoluble in water, having an amount of A to E of 100% by weight, and by polymerizing the components of the total mixture of carbohydrate components and monoethylenically unsaturated monomers either rather or in parts and that the residue is added after or that all ingredients are added in batches. 8. The use of graft copolymers binding multivalent metal ions. by claims 1 to 6 for 9. Use of vaccinees inhibition of water hardness. copolymers by claims 1 to 6 na 10. Use of vaccinees copolymers by of claims 1 to 6 than an additive component in detergents and cleaning agents. Use of the graft copolymers according to claims 1 to 6 as an additive component in washing solutions. .ŕ • Use of the graft copolymers according to claims 1 to 6 as a finishing aid in textiles. Use of the graft copolymers according to claims 1 to 6 as an auxiliary agent in the pretreatment of raw fibrous materials or textiles. Use of the graft copolymers according to claims 1 to 6 as an auxiliary agent in the welding, scouring and bleaching of raw fibrous materials, fibers and textiles. Use of the graft copolymers according to claims 1 to 6 as an aid in dyeing natural and / or synthetic fibers or textiles. alternate side Use of the graft copolymers according to claims 1 to 6 as a fabric printing aid, in particular in the washing of reactive printing dyes and vat dyes of natural and / or synthetic fibers or textiles. Use of the graft copolymers according to claims 1 to 6 as an auxiliary agent for degreasing natural or synthetic ... woven or textile. Use of the graft copolymers according to claims 1 to 6 as an auxiliary agent according to claims 12 to 17, characterized in that they are used in combination with surfactants, in particular anionic surfactants. Use of graft copolymers according to claims 1 to 6 as auxiliary agent according to claims 12 to 18, characterized in that they are used in combination with complexing carboxylic acids. Use of graft copolymers according to claims 1 to 6 as an auxiliary agent according to claims 13 and 14, 18 and 19, characterized in that they are used in chlorine-free bleaching with preference for a multi-stage process in an adjustable treatment bath or in such continuous processes. Use of graft copolymers according to claims 1 to 6 in the production of pigment and dye dispersions. Use of the graft copolymers according to claims 1 to 6 as a paper processing aid for the production of pigment and filler coatings. Use of the graft copolymers according to claims 1 to 6 as a processing aid for the skin.