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WO1992010433A1 - Utilisation de substances naturelles greffees solubles dans l'eau comme agents de traitement des eaux - Google Patents

Utilisation de substances naturelles greffees solubles dans l'eau comme agents de traitement des eaux Download PDF

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Publication number
WO1992010433A1
WO1992010433A1 PCT/EP1991/002225 EP9102225W WO9210433A1 WO 1992010433 A1 WO1992010433 A1 WO 1992010433A1 EP 9102225 W EP9102225 W EP 9102225W WO 9210433 A1 WO9210433 A1 WO 9210433A1
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Prior art keywords
polysaccharides
monomers
acid
weight
water
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PCT/EP1991/002225
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German (de)
English (en)
Inventor
Walter Denzinger
Heinrich Hartmann
Charalampos Grousetis
Karl-Heinz Buechner
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Basf Aktiengesellschaft
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Publication of WO1992010433A1 publication Critical patent/WO1992010433A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen

Definitions

  • the invention relates to the use of water-soluble grafted natural products which can be obtained as water treatment agents by polymerizing monoethylene-unsaturated carboxylic acids and optionally other monomers in the presence of monosaccharides, oligosaccharides, polysaccharides and / or derivatives thereof.
  • Low-molecular-weight copolymers are known from US Pat. No. 3,755,264, which contain 85 to 99 mol% of maleic anhydride and, in addition to 100 mol% of acrylic acid, vinyl acetate, styrene or mixtures thereof, copolymerized.
  • the copolymers are prepared by copolymerizing maleic anhydride in dry organic solvents with the monomers mentioned at temperatures from 100 to 145 ° C. in the presence of peroxides. Examples of suitable peroxides are di-tertiary-butyl peroxide, acetyl peroxide, dicumyl peroxide, diisopropyl percarbonate and, in particular, benzoyl peroxide.
  • the anhydride groups of the copolymer can be hydrolyzed to acid groups or converted into the salts after the polymerization.
  • the water-soluble copolymers are used to prevent scale deposition. The ones obtainable by this procedure
  • JP-A-61/031 498 discloses detergents which contain 0.5 to 50% by weight of graft polymers of a monosaccharide and / or an oligosaccharide and a water-soluble ethylenically unsaturated monomer as binders. According to the examples, acrylic acid was grafted onto sucrose or glucose.
  • the graft copolymers are used as additives for washing and cleaning agents in amounts of 0.1 to 20% by weight, based on the respective formulations.
  • the invention is based on the object of providing agents for water treatment which achieve or even exceed the effect of the polymers based on acrylic acid used hitherto and which can be prepared with the partial use of renewable raw materials.
  • the graft polymers can be obtained by homo- or copolymerization of the monomers (A) in the presence of the natural products (B).
  • Monoethylenically unsaturated C3- to Cio-monocarboxylic acids and their alkali and / or ammonium salts are suitable as monomers of group (a).
  • These monomers include, for example, acrylic acid, methacrylic acid, diethyl acrylic acid, ethyl acrylic acid, allylacetic acid and vinyl acetic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, their mixtures and the sodium, potassium or ammonium salts or mixtures thereof.
  • These monomers are used either alone or in a mixture with monoethylenically unsaturated dicarboxylic acids or their anhydrides in the presence of
  • Natural substances (B) poly erized.
  • Such dicarboxylic acids contain 4 to 8 carbon atoms, for example maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylene malonic acid, citraconic acid, maleic acid anyhdrid, itaconic acid anhydride and methylene malonic acid anhydride.
  • the monoethylenically unsaturated C4- to C ⁇ -dicarboxylic acids can be used in the form of the free acids or in a form neutralized with alkali metal bases, ammonia or amines in the graft polymerization.
  • maleic acid, maleic anhydride, itaconic acid or itaconic anhydride and the sodium, potassium or ammonium salts of maleic acid or itaconic acid are preferably used.
  • These salts can be obtained, for example, from maleic anhydride or itaconic anhydride if the anhydrides mentioned are neutralized in aqueous solution with sodium hydroxide solution, potassium hydroxide solution or ammonia or amines.
  • the cited dicarboxylic acids or their anhydrides or their salts can also be polymerized alone in the presence of the natural substances (B). Of particular interest are those graft polymers which are obtained by copolymerization of
  • the monomers of group (a) can optionally be subjected to the graft copolymerization together with (b) other monoethylenically unsaturated monomers which can be copolymerized with the monomers (a).
  • the proportion of the monomers (a) in the monomer mixture (A) is 40 to 100% by weight, while the monomers (b) can be present in it up to 60% by weight.
  • the monomers of group (b) which may be used in the graft copolymerization include, for example, C 1 -C 6 -alkyl and hydroxyalkyl esters of the compounds mentioned under (a), for example methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl ethacrylate, maleic acid monomethyl ester, maleic acid dimethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
  • C 1 -C 6 -alkyl and hydroxyalkyl esters of the compounds mentioned under (a) for example methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl ethacrylate, maleic acid monomethyl ester, maleic acid dimethyl ester
  • the amides and N-substituted alkylamides of the compounds given under (a) come as monomers Group (b), for example acrylamide, methacrylic acid, NA kylacrylamide with 1 to 18 carbon atoms in the alkyl group, such as N-methylacrylamide, N, N-dimethylacrylamide, N-tert-butylacrylamide, N-octadecylacrylamide, Maleic acid monoethylhexylamide, maleic acid monododecylamide, dimethylaminopropyl methacrylic acid and acrylamidoglycolic acid.
  • Group (b) for example acrylamide, methacrylic acid, NA kylacrylamide with 1 to 18 carbon atoms in the alkyl group, such as N-methylacrylamide, N, N-dimethylacrylamide, N-tert-butylacrylamide, N-octadecylacrylamide, Maleic acid monoethylhexylamide, maleic
  • alkyl inoalkyl (meth) acrylates for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethyla inopropyl acrylate and dimethylaminopropyl methacrylate.
  • monomers of group (b) are monomers containing sulfo groups, such as, for example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and acrylic idomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid and acrylamide, allyl phosphonic acid .
  • sulfo groups such as, for example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and acrylic idomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid and acrylamide, allyl phosphonic acid
  • This group of monomers also includes N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, 1-vinylimidazole, 1-vinyl-2-methylimidazole, vinyl acetate and vinyl propionate.
  • monomers of group (b) are the esters of alkoxylated C 1 -C 14 -alcohols which have been reacted with 2 to 50 mol of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with the monoethylenically unsaturated carboxylic acids of group (a), e.g.
  • esters of acrylic acid, methacrylic acid or maleic acid with a C ⁇ 3 / Ci5 oxo alcohol which has been reacted with different amounts of ethylene oxide, e.g. 3 moles, 5 moles, 7 moles, 10 moles or 30 moles of ethylene oxide.
  • the basic monomers are preferably in the form of salts with mineral acids, e.g. Hydrochloric acid, sulfuric acid or nitric acid, or used in quaternized form (suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride).
  • Rl R_o- (CH-CH-0) n _ ⁇ -CH-CH-,
  • R3, R H, CH 3 , C 2 H 5 ,
  • R C ** .- to C 2 8-alkyl
  • n 2 to 100
  • the preferred monomers of group (b) are hydroxyethyl acrylate, hydroxypropyl acrylates, vinyl acetate, N-vinylpyrrolidone, acrylamidomethylpropanesulfonic acid and N-vinylimidazole.
  • a further modification of the graft copolymers can be achieved by carrying out the graft polymerization in the presence of monomers from group (c).
  • the monomer mixtures contain up to 5% by weight of a monomer having at least two ethylenically unsaturated non-conjugated double bonds in the molecule.
  • These compounds are usually used as crosslinkers in copolymerizations. They can be added to the monomers of group (a) used for the copolymerization or to the monomer mixtures from (a) and (b). If they are used, the amount of monomers (c) used is preferably 0.05 to 2% by weight.
  • Suitable compounds of this type are, for example, methylene bisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, for example glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and at least polyols esterified with acrylic acid or methacrylic acid, such as pentaerythritol and Glucose.
  • Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds, preference is given to using water-soluble monomers, such as glycol diacrylate or glycol diacrylates of polyethylene glycols having a molecular weight of up to 3,000.
  • the monomers (a) and, if appropriate, additionally (b) and (c) are polymerized in the presence of natural products based on polysaccharides, oligosaccharides, monosaccharides and their derivatives.
  • the natural substances are e.g. Saccharides of vegetable or animal origin or products of the metabolism of microorganisms and their degradation and modification products which are already dispersible or soluble in water or alkalis or during the polymerization of the monomers (a) and optionally (b) and (c) become dispersible or soluble directly or partially or completely neutralized with alkalis, ammonia or amines.
  • pectin algin, chitin, chitosan, heparin, carrageenan, agar, gum arabic, tragacanth, karaya gum, ghatti gum, locust bean gum, guar gum, tara gum, inulin, xanthan, dextran, nigeran and pentosans such as xylan and araban, the main components of which are D-glucuronic acid, D-galacturonic acid, D-galacturonic acid methyl ester, D-mannuronic acid, L-guluronic acid, D- and L-galactose, 3,6-anhydro-D-galactose, L-arabinose , LR-hamnose, D-glucuronic acid, D-xylose, L-fucose, D-mannose, D-fructose and D-glucose, 2-amino-2-deoxi-D-glucose and 2-amino-2-deoxi-
  • the polysaccharides of component (B) used in the graft copolymerization are preferably starch, thermally and / or mechanically treated starch, oxidatively, hydrolytically or enzymatically degraded starches, oxidized hydrolytically or oxidized enzymatically degraded starches, and chemically modified starches and chemically modified starches Monosaccharides and oligosaccharides.
  • starches from corn, wheat, rice, tapioca and in particular starch from potatoes are preferred.
  • the starches are practically insoluble in water and can be prepared in a known manner by thermal and / or mechanical treatment or by an enzymatic or an acid-catalyzed degradation in a water-soluble form.
  • Oxidatively degraded starches are also suitable as component (B).
  • the following compounds may be mentioned as starch breakdown products, which are obtainable either by oxidative, hydrolytic or enzymatic breakdown of starch: dextrins, such as white and yellow dextrins, maltodextrins, glucose syrups, maltose syrups, hydrolysates with a high content of D-glucose, starch saccharification products and the like Maltose and D-glucose and their iso erization product fructose.
  • Mono- and oligosaccharides such as galactose, mannose, ribose, sucrose, raffinose, lactose and trehalose, and cellulose degradation products, for example cellobiose and its oligomers, are of course also suitable as component (B).
  • Oxidized starches such as e.g. Dialdehyde starch and oxidized starch degradation products, such as gluconic acid, glucaric acid and glucuronic acid.
  • Oxidized starches such as e.g. Dialdehyde starch and oxidized starch degradation products, such as gluconic acid, glucaric acid and glucuronic acid.
  • Such compounds are obtained, for example, by oxidizing starch with periodate, chromic acid, hydrogen peroxide, nitrogen dioxide, nitrogen tetroxide, nitric acid or hypochlorite.
  • component (B) are chemically modified polysaccharides, in particular chemically modified starches, for example starches and starch degradation products converted with acids to esters and with alcohols to ethers.
  • the esterification of these substances is possible both with inorganic and with organic acids, their anhydrides or chlorides. In the case of direct esterification, the water released leads to acid-catalyzed cleavage of glycosidic bonds.
  • Phosphated and acetylated starches and starch breakdown products are of particular technical interest.
  • the most common method for etherifying starch is to treat the starch and starch degradation products with organic halogen compounds, epoxides or sulfates in aqueous alkaline solution.
  • Starch ethers are, for example, the alkyl ether, hydroxyalkyl ether, carboxyalkyl ether and allyl ether of starch.
  • Chemically modified starches according to component (B) are also to be understood as meaning cationically modified starches, for example starches reacted with 2,3-epoxypropyltrimethylammonium chloride, as described, for example, in US Pat. No. 3,649,616.
  • Chemically modified polysaccharides also include, for example, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, sulfoethyl cellulose, carboxymethyl sulfoethyl cellulose, hydroxypropyl sulfoethyl cellulose, hydroxyethyl sulfoethyl cellulose, methyl sulfoethyl cellulose and ethyl sulfo cellulose.
  • Chemically modified degraded starches are also suitable as component (B), for example hydrogenation products of starch hydrolysates such as sorbitol and mannitol, maltitol and hydrogenated glucose syrups or oxidized hydrolytically degraded or oxidized enzymatically degraded starches.
  • the products of acid-catalyzed or enzymatic transglycosidation or glycosidation such as e.g. Methyl glucose.
  • the monomers (a) and optionally (b) and / or (c) are radically polymerized in the presence of compounds of component (B).
  • compounds of component (B) may be favorable for the effect of the graft polymer formed to use two or more of the compounds indicated under (B), e.g. Mixtures of acid-catalytically or enzymatically degraded starches and gluconic acid, mixtures of a monosaccharide and an oligosaccharide, mixtures of an enzymatically degraded starch and a monosaccharide or mixtures of glucose and sucrose or mannose.
  • the polymerization can be carried out in the presence or in the absence of inert solvents or inert diluents. Since the polymerization in the absence of inert solvents or diluents usually leads to inconsistent graft polymers, the graft polymerization in an inert solvent or diluent is preferred.
  • Suitable inert diluents are, for example, in which the compounds indicated under (B) can be suspended and which dissolve the monomers (A). In these cases, the graft polymers are in suspended form after the polymerisation and can easily be isolated by filtration in solid form.
  • Suitable inert diluents are, for example, toluene, o-, m-, p-xylene and
  • Isomer mixtures ethylbenzene, aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, nonane, DodeGan, cyclohexane, Cyclooctane, methylcyclohexane and mixtures of the hydrocarbons mentioned or gasoline fractions which do not contain any polymerizable monomers.
  • Chlorinated hydrocarbons such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane and tetrachloroethane are also suitable.
  • anhydrous compounds of component (B) are used and the anhydrides from the group of monomers (a) are preferably used.
  • a preferred way of producing the graft polymers is solution polymerization, the compounds of component (B), the monomers (A) and the graft copolymer formed being at least dispersed, preferably in dissolved form.
  • Inert solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tetrahydrofuran, dioxane, and mixtures of the inert solvents mentioned are suitable, for example, for solution polymerization.
  • the copolymerization can be carried out continuously or batchwise.
  • components (A) and (B) can also be copolymerized in the absence of inert diluents or solvents. Continuous polymerization at temperatures of 160 to 250 ° C. is particularly suitable for this. If necessary, it is possible to work in the absence of polymerization initiators.
  • catalysts which form free radicals under the polymerization conditions for example inorganic and organic peroxides, persulfates, azo compounds and so-called redox catalysts.
  • the graft polymers are generally prepared using free-radical initiators.
  • Suitable radical initiators are preferably all those compounds which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If you start the polymerization initially at a lower temperature and at a higher temperature to an end, it is expedient to work with at least two decompose at different temperatures ver ⁇ initiators, namely, first one at a relatively low temperature decomposed • falling for initiating use the polymerization and then end the main polymerization with an initiator lead, which disintegrates at a higher temperature. Water-soluble and water-insoluble initiators or mixtures of water-soluble and water-insoluble initiators can be used. The water-insoluble initiators are then soluble in the organic phase. The initiators listed for this purpose can be used, for example, for the temperature ranges specified below.
  • salts or complexes of heavy metals for example copper, cobalt, manganese, iron, vanadium, cerium, nickel and chromium salts or organic compounds such as benzoin, dimethylaniline or Ascorbic acid
  • the half-lives of the radical initiators indicated can be reduced.
  • tert-butyl hydroperoxide with the addition of 5 ppm copper II acetylacetonate can already be activated in such a way that polymerisation can take place at 100 ° C.
  • the reducing component of redox catalysts can also be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine.
  • a polymerization initiator or a mixture of several polymerization initiators is used.
  • 0.01 to 5% of the reducing compounds are added as redox components.
  • Heavy metals are used in the range of 0.1 to 100 ppm, preferably 0.5 to 10 ppm. It is often advantageous to use a combination of peroxide, reducing agent and heavy metal as a redox catalyst.
  • the polymerization of the monomers (a) and the optionally used monomers (b) and / or (c) can also be carried out by the action of ultraviolet radiation, if appropriate in the presence of UV initiators.
  • the photoinitiators or sensitizers that are normally used are used. These are, for example, compounds such as benzoin and benzoin ether, ⁇ -methylbenzoin or ⁇ -phenylbenzoin. So-called triplet sensitizers, such as benzene diketals, can also be used.
  • high-energy UV lamps such as carbon arc lamps, mercury vapor lamps or xenon lamps
  • low-UV light sources such as fluorescent tubes with a high proportion of blue, also serve as UV radiation sources.
  • Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercapto-butanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan.
  • allyl compounds such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols. If the polymerization is in the presence of regulators is carried out, 0.05 to 20% by weight, based on the monomers used in the polymerization, are required.
  • the polymerization is carried out in the presence of water-soluble phosphorus compounds in which the phosphorus has an oxidation number of 1 to 4, the water-soluble alkali metal or ammonium salts, water-soluble Compounds containing PO (OH) 2 groups and / or their water-soluble salts.
  • Phosphorous acid is preferably used.
  • the phosphorus compounds in question are used to reduce the discoloration of the graft copolymers in amounts of from 0.01 to 5% by weight, based on the monomers (A) used.
  • the phosphorus compounds in question are described in EP-A-0 175317.
  • the copolymerization of components (A) and (B) is usually carried out in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization.
  • the reaction participants which are preferably present in an inert diluent, can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature. These temperatures are in the range of 40 to 150 ° C. With this method, however, graft copolymers are obtained which, when using dicarboxylic acids, have a relatively high content of unpolymerized dicarboxylic acid.
  • the monomers (A) are therefore added to the polymerizing mixture continuously or batchwise after the polymerization has started, to the extent that the graft polymerization can be easily controlled in the desired temperature range .
  • a type of addition of the monomers of component (A) is preferred in which the compounds of component (B) or at least some of the compounds of component (B) are first combined with at least one monomer of group (a ) placed in the reactor and heated to the desired polymerization temperature with stirring. As soon as this temperature is reached, the remaining monomers of group (a) are added over a period of about 1 to 10, preferably 2 to 8 hours.
  • Such a procedure is used, for example, when polymerizing components (A) and (B) in an inert diluent in which component (B) is suspended and also in graft copolymerization carried out in solution.
  • the graft copolymers are preferably prepared by suspension or solution polymerization of components (A) and (B) in an aqueous medium, with solution polymerization in water being particularly preferred.
  • solution polymerization in an aqueous medium the procedure is, for example, that the monomers (a) and at least some of the compounds of component (B) are initially introduced in an aqueous medium and, if appropriate, the remaining monomers of group (a) and, if appropriate, the
  • Monomers (b) and, if appropriate, the monomers (c) are added continuously or batchwise to the polymerizing reaction mixture and copolymerized in such a way that the degree of neutralization of the copolymerized monomer units (1) and (2) of the monomers of group (a) after completion of the graft copolymerization, ie when at least 95, preferably 98-99% of the monomers have polymerized, is 20 to 80%.
  • the monomers (1) of group (a) are preferably used in at least 20% neutralized form at the start of the polymerization.
  • the entire amount of the compounds of component (B) or only a part, for example 50%, of the compounds of component (B) together with the monomers (1) of group (a) and the remainder Add amounts of compounds of component (B) to the polymerizing reaction mixture together with the monomers (2) from group (a) and, if appropriate, the monomers (b) and / or (c) continuously or batchwise.
  • the monomers (2) from group (a) ie in particular maleic acid
  • the monomers (1) and (2) of group (a) can be partially neutralized so that their degree of neutralization is in each case in the range specified.
  • Monomer is used, for example acrylamido methyl propanesulfonic acid or vinylphosphonic acid, during the
  • a base e.g. Add sodium hydroxide solution, potassium hydroxide solution, ammonia or ethanolamine.
  • the solution copolymerization is particularly preferably carried out with hydrogen peroxide, sodium persulfate or mixtures in any ratio as initiator. This requires 0.5 to 20% by weight of initiator, based on the monomers (A).
  • the monomer mixture (A) consists of a small proportion of the monomers (1) of group (a)
  • a relatively low amount of initiator is used and if the proportion of monomers (1) of group (a) is high, a larger amount of initiator is used, e.g. for 90% by weight of monomer (1) of group (a) about 15 to 18% by weight of initiator.
  • the procedure is such that at least a portion of component (B) is initially introduced together with the monomers (1) from group (a), which are preferably at least 90% neutralized, and the monomers (2) from the group (a) and optionally the monomers (b) and / or (c) while maintaining the required degree of neutralization of 20 to 80%.
  • the monomers (2) of group (a) can be neutralized either by adding appropriate amounts of base separately or by adding partially neutralized monomers (2) from group (a) to the reaction mixture.
  • the degree of neutralization of the partially neutralized monomers (2) of group (a) is then in the range from 20 to 80%.
  • polysaccharides in aqueous suspension can be subjected to the graft copolymerization.
  • graft copolymers from polysaccharides are preferably prepared by first converting a water-insoluble polysaccharide in aqueous suspension with the addition of enzymes and / or acids to a water-soluble form, and the aqueous solution of the degraded polysaccharide obtained in this way Subject to graft copolymerization.
  • a water-insoluble polysaccharide such as potato starch, is first suspended in water and broken down.
  • This degradation can be carried out under the action of enzymes, for example ⁇ - or ⁇ -amylase, or of debranching enzymes, for example pullulanase, or by the action of inorganic or organic acids in a known manner.
  • Suitable inorganic acids are, for example, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.
  • Suitable organic acids are, for example, saturated or unsaturated carboxylic acids, for example formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, p-toluenesulfonic acid and benzenesulfonic acid.
  • the conversion of the polysaccharides into a water-soluble form is preferably carried out with a monomer (a), which is then used in the graft copolymerization.
  • a monomer (a) for example, potato starch or maize starch can be hydrolytically degraded in an aqueous suspension by adding acrylic acid, methacrylic acid, maleic acid or itaconic acid in the temperature range from 50 to 150 ° C.
  • the added monocarboxylic acid or maleic acid or itaconic acid is neutralized to at least 20, preferably 90%, and by adding the remaining monomers of group (a) and optionally monomers (b) and, if appropriate (c) the graft copolymerization was carried out.
  • the enzymatic degradation of starch is carried out in the temperature range from 30 to 120 ° C, while the hydrolytic degradation of the starch is carried out at temperatures from 50 to 150 ° C.
  • the hydrolytic degradation takes about 5 minutes to 10 hours, the degree of hydrolytic degradation of the starch depending on the selected temperature, pH and time. Further information on the breakdown of starch can be found in the specialist literature, cf. e.g. Günther Tegge, starch and starch derivatives, Behr's Verlag, Hamburg 1984.
  • it has proven advantageous to use at least one of the phosphorus compounds already in the enzymatic or hydrolytic degradation of the starch which according to the teaching of EP-A-0 175 317 lead to polymers which are not or only very slightly colored.
  • the temperatures are usually in the range from 40 to 180, preferably 60 to 150 ° C. As soon as the temperature in the copolymerization is above the boiling points of the inert diluent or solvent or the monomers, the copolymerization is carried out under pressure.
  • the concentration of components (A) and (B) in the copolymerization in the presence of inert solvents or inert diluents is 10 to 80, preferably 20 to 70,% by weight.
  • the graft copolymers can be prepared in the customary polymerization devices. For this purpose, for example, stirred kettles are used which are equipped with an anchor, blade, impeller or multi-stage impulse countercurrent stirrer.
  • graft copolymerization in the absence of diluents, it can be advantageous to carry out the graft copolymerization in kneaders. It may also be necessary to polymerize in a kneader when working at high concentrations or when the natural products are high molecular weight and initially swell strongly.
  • graft copolymers with K values of 8 to 70, preferably 10 to 40, (measured on 1% strength aqueous solutions of the copolymers at pH 7 and 25 ° C.).
  • the graft copolymers which can be prepared by the processes given above are colorless to brownish-colored products. When polymerizing in an aqueous medium, they are present as dispersions or polymer solutions. Depending on the particular composition and the concentration of the graft copolymers, these are low-viscosity to pasty aqueous solutions or dispersions.
  • the graft polymers described above are more biodegradable due to the natural substance content than the previously used copolymers based on ethylenically unsaturated monomers, but at least can be eliminated with the sewage sludge from sewage treatment plants.
  • aqueous copolymer solutions obtainable in this way can be used directly as water treatment agents for reducing scale deposition and water hardness excretion in water-bearing systems. It is possible to combine the polymers according to the invention with other dispersants, such as phosphonates, phosphonoalkane carboxylic acids etc.
  • the mode of action of the graft polymers as so-called scale inhibitors for water treatment consists in the formation of crystals of the hardener salts, such as calcium carbonate, To prevent magnesium oxide, magnesium carbonate, calcium, barium or strontium sulfate, calcium phosphate (apatite) and the like in the sub-stoichiometric dosage range or to influence the formation of these precipitates in such a way that no hard and stone-like deposits are formed, but rather easy-to-wash out, finely divided precipitates are formed become. In this way, the surfaces of, for example, heat exchangers, pipes or pump components are kept free of deposits and their tendency to corrode is reduced. In particular, the risk of pitting corrosion under these coverings is reduced.
  • the hardener salts such as calcium carbonate
  • the amounts of deposit inhibitor required for this are 0.1 to 100, preferably 0.5 to 25 ppm, based on the respective amount of water.
  • the water-carrying systems are, for example, open or closed cooling circuits, for example of power plants or chemical plants, such as reactors, distillation apparatuses and similar components, in which heat has to be removed.
  • These deposit inhibitors can also be used in boiler water and steam generators, preferably in the range of water temperatures below 150 ° C.
  • a preferred application of the scale inhibitors to be used according to the invention is also the desalination of sea and brackish water by distillation or membrane processes, such as reverse osmosis or electrodialysis.
  • distillation or membrane processes such as reverse osmosis or electrodialysis.
  • MSF distillation process multi-day rash evaporation
  • thickened sea water is circulated at elevated temperature for desalination.
  • the deposit preventers effectively prevent the excretion of hardness-forming agents, such as brucite, and their caking on plant components.
  • a further application of the deposit inhibitor is, for example, when evaporating sugar juices from cane or beet sugar.
  • the sugar thin juice is cleaned here, for example, calcium hydroxide, carbon dioxide, sulfur dioxide. if phosphoric acid is added.
  • the remaining slightly soluble calcium salts such as calcium carbonate, sulfate or phosphate, precipitate out during the evaporation process and can appear as rock hard deposits on heat exchanger surfaces.
  • copolymers which can be used according to the invention as deposit inhibitors are able to largely prevent the above-mentioned deposit formation, so that downtimes of the systems for cleaning, e.g. by boiling out, can be significantly reduced.
  • An important aspect here is the considerable energy saving by avoiding the heat-insulating coverings mentioned.
  • the amounts of deposit inhibitor required in the applications described are different, but are between 0.1 and 100 ppm, based on the cooling water, boiler water, process water or e.g. Sugar juice.
  • the products to be used according to the invention have better dispersion compared to hardness-forming salts, such as calcium carbonate, calcium sulfate and calcium phosphate, and are also more compatible with calcium ions than acrylic acid copolymer.
  • the K values of the copolymers were determined according to H. Fikentscher, Cellulosechemie, Vol. 13, 48 to 64 and 71 to 74 (1932) in aqueous solution at a pH of 7, a temperature of 25 ° C and a polymer concentration of the sodium salt of Copolymer determined from 1 wt.%. The percentages relate to the weight of the fabrics. Examples
  • the yellowish polymer solution obtained has a solids content of 46.8% and a pH of 7.0.
  • the K value of the graft polymer is 14.6.
  • Feed devices, and a distillation device is provided, 1056 g of a mixture of isopropanol and water in a ratio of 75:25, 806.46 g of maltodextrin with a DE value (according to Luff-Schoorl) of 11 to 14, 94% and 47, 16 g of 30% hydrogen peroxide are initially charged.
  • the reactor is then pressed off 3 times with 3 bar nitrogen and expanded again and then heated to 120 ° C., a pressure of 3 bar being established.
  • the maleic acid and acrylic acid units contained in the graft copolymer have a degree of neutralization of 50.6%. After the hydrogen peroxide addition has ended, the reaction mixture is heated to boiling for a further hour and neutralized by adding 137 g of 50% strength aqueous sodium hydroxide solution. A clear, viscous, brown solution with a solids content of 39% is obtained.
  • the graft copolymer has a K value of 31.5.
  • the mixture is then neutralized to a pH of 8 by adding 50% aqueous sodium hydroxide solution. Now it is cooled and the 50.6% almost clear solution is adjusted to 45% by dilution with water, the K value of the graft polymer is 23.5.
  • Water treatment agent 2 Commercial homopolymer of acrylic acid with a K value of 20.
  • the graft polymers described above are subjected to the following tests for their suitability as water treatment agents and compared with commercially available water treatment agents.
  • An aqueous test solution is prepared from components A and B.
  • the data on polymer refer to 100% substance.
  • the graft polymers have an improved effectiveness in comparison with the homopolymers of acrylic acid with a comparable K value.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Utilisation de polymères greffés solubles dans l'eau, obtenus par polymérisation, amorcée par des radicaux, (A) de mélanges monomèrs qui renferment, comme monomères principaux, des acides carboxyliques mono-éthylèniquement insaturés, des sels alcalins et/ou des sels d'ammonium de ces acides, en présence (B) de monosaccharides, d'oligosaccharides, de polysaccharides, de polysaccharides dégradés par oxydation, par hydrolyse ou par voie enzymatique, de polysaccharides dégradés par hydrolyse oxydante ou par voie enzymatique oxydante, de monosaccharides, d'oligosaccharides et de polysaccharides modifiés chimiquement, ou de mélanges des composés précités, dans un rapport en poids (A):(B) de (95 à 20):(5 à 80), comme agents de traitement des eaux.
PCT/EP1991/002225 1990-12-06 1991-11-26 Utilisation de substances naturelles greffees solubles dans l'eau comme agents de traitement des eaux WO1992010433A1 (fr)

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DE19904038908 DE4038908A1 (de) 1990-12-06 1990-12-06 Verwendung von wasserloeslichen gepfropften naturstoffen als wasserbehandlungsmittel
DEP4038908.1 1990-12-06

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DE4343993A1 (de) * 1993-12-22 1995-06-29 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Polyhydroxyverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19619680A1 (de) * 1996-05-15 1997-11-20 Buna Sow Leuna Olefinverb Gmbh Verfahren zur Herstellung von superabsorbierenden Polymeren auf Stärkebasis
CN1048259C (zh) * 1992-07-02 2000-01-12 施托克豪森化学制造有限公司 不饱和单体和糖类的接枝共聚物,它们的生产方法及其应用
WO2007006521A3 (fr) * 2005-07-12 2007-07-19 Isagro Spa Mélanges nutritionnels à efficacité élevée et accrue
US8354368B2 (en) 2008-06-24 2013-01-15 Cognis Ip Management Gmbh Cleaning composition comprising graft copolymers
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same
CN118561436A (zh) * 2024-06-26 2024-08-30 北京鹏发环保集团有限公司 一种高效缓蚀阻垢剂及其制备方法

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FR2761366A1 (fr) * 1997-03-26 1998-10-02 Synthron Nouveaux copolymeres greffes amphoteres a biodegradabilite amelioree utilisables comme agents dispersants
KR101107581B1 (ko) * 2003-12-03 2012-01-25 도아고세이가부시키가이샤 수용성 폴리머의 제조방법
US7666963B2 (en) 2005-07-21 2010-02-23 Akzo Nobel N.V. Hybrid copolymers
NO20073821L (no) 2006-07-21 2008-01-22 Akzo Nobel Chemicals Int Bv Podede kopolymerer med lav molekylvekt
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
CN108585228B (zh) * 2018-04-07 2021-09-03 侯文燕 一种海藻多糖高效锅炉水调节剂
CN113880265B (zh) * 2021-10-25 2023-06-20 青岛大学 一种无磷缓蚀阻垢剂及其制备方法

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1048259C (zh) * 1992-07-02 2000-01-12 施托克豪森化学制造有限公司 不饱和单体和糖类的接枝共聚物,它们的生产方法及其应用
DE4343993A1 (de) * 1993-12-22 1995-06-29 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Polyhydroxyverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19619680A1 (de) * 1996-05-15 1997-11-20 Buna Sow Leuna Olefinverb Gmbh Verfahren zur Herstellung von superabsorbierenden Polymeren auf Stärkebasis
WO2007006521A3 (fr) * 2005-07-12 2007-07-19 Isagro Spa Mélanges nutritionnels à efficacité élevée et accrue
US9321873B2 (en) 2005-07-21 2016-04-26 Akzo Nobel N.V. Hybrid copolymer compositions for personal care applications
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
EP2138560B2 (fr) † 2008-06-24 2015-04-01 Cognis IP Management GmbH Produit de nettoyage contenant des copolymères greffés
US8354368B2 (en) 2008-06-24 2013-01-15 Cognis Ip Management Gmbh Cleaning composition comprising graft copolymers
US9309489B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US9309490B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer compositon and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US10053652B2 (en) 2014-05-15 2018-08-21 Ecolab Usa Inc. Bio-based pot and pan pre-soak
CN118561436A (zh) * 2024-06-26 2024-08-30 北京鹏发环保集团有限公司 一种高效缓蚀阻垢剂及其制备方法

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