EP0469018A1 - Copolymeres a base d'anhydrides d'acide bicarbonique monoethyleniquement insatures, de dicetene et d'acides monocarboniques monoethyleniquement insatures; production et utilisation de ces copolymeres - Google Patents

Copolymeres a base d'anhydrides d'acide bicarbonique monoethyleniquement insatures, de dicetene et d'acides monocarboniques monoethyleniquement insatures; production et utilisation de ces copolymeres

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Publication number
EP0469018A1
EP0469018A1 EP90906186A EP90906186A EP0469018A1 EP 0469018 A1 EP0469018 A1 EP 0469018A1 EP 90906186 A EP90906186 A EP 90906186A EP 90906186 A EP90906186 A EP 90906186A EP 0469018 A1 EP0469018 A1 EP 0469018A1
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EP
European Patent Office
Prior art keywords
copolymers
mol
monoethylenically unsaturated
acid
monomers
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EP90906186A
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German (de)
English (en)
Inventor
Dieter Boeckh
Hans-Peter Seelmann-Eggebert
Heinrich Hartmann
Wolfgang Trieselt
Alexander Kud
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BASF SE
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BASF SE
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Publication of EP0469018A1 publication Critical patent/EP0469018A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/36—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by a ketonic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts

Definitions

  • Copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides such as maleic anhydride, diketene and C 1 -C 22 -alkyl vinyl ethers, are known from US Pat. No. 4,009,110. These copolymers can also. are in partially hydrolyzed form.
  • the at least partially hydrolyzed copolymers are used, for example, as surface-active compounds, as glass cleaners or as builders for solid and liquid detergents. According to the information in the examples, the copolymers are used in amounts of 7.5 to 30% by weight in detergent formulations.
  • the copolymers act as builders, prevent dirt from re-accumulating on the washed textiles when washing textile materials and have a certain calcium complex binding capacity.
  • EP-PS 00 25 551 discloses the use of copolymers of 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid or their alkali metal or ammonium salts as incrustation inhibitors in detergents.
  • the copolymers are contained in amounts of 0.5 to 10% by weight.
  • the copolymers are very effective incrustation inhibitors, it is not possible to prepare stable liquid detergent formulations with them, because a phase separation occurs after a relatively short time.
  • the present invention has for its object to provide improved polymeric additives for liquid and powder detergent formulations.
  • copolymerizable monomer mixtures containing monoolefinically unsaturated comonomers are copolymerized in a solvent which is inert to the monomers in the presence of polymerization initiators at from 40 to 160 ° C. and the copolymers are isolated or the anhydride and ketene groups of the copolymers are hydrolyzed, if appropriate.
  • Component a) of the copolymers are monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 8 carbon atoms, e.g. Maleic anhydride, itaconic anhydride, mesaconic anhydride, citraconic anhydride and methylene malonic anhydride.
  • the copolymers contain 10 to 60, preferably 20 to 50 mol.% Of at least one of the dicarboxylic acid anhydrides mentioned in polymerized form.
  • the copolymers contain as component b) 5 to 60, preferably 10 to 40, mol% of diketene copolymerized.
  • the copolymers contain, as component (c), at least one monoethylenically unsaturated C 3 - to C 8 -monocarboxylic acid polymerized in, for example acrylic acid, methacrylic acid, vinyl acetic acid, allylacetic acid, propylidene acetic acid, ethylidene acetic acid, crotonic acid, ⁇ , ⁇ -ethyl acrylic acid and ⁇ , ⁇ -Dimethylacrylic acid. From this group of monomers, acrylic acid and methacrylic acid are preferably used.
  • anhydrides are accessible from these carboxylic acids, for example Methacrylic anhydride and acrylic anhydride, these anhydrides can also be used in the copolymerization.
  • the monomers of group c) make up 0.5 to 60, preferably 5 to 50, mol% of the copolymers.
  • (c) contain 5 to 50 mol.% of acrylic acid, methacrylic acid or mixtures of acrylic acid and methacrylic acid in copolymerized form.
  • a further modification of the copolymers can be achieved by copolymerization in the presence of monomers
  • Group (d) carries out. These include other monoethylenically unsaturated monomers that are different from the monomers of groups (a), (b) and (c).
  • monoethylenically unsaturated monomers that are different from the monomers of groups (a), (b) and (c).
  • the basic monomers k can be used in the form of the free bases as well as in neutralized or quaternized form in the copolymerization.
  • the monomers of group (d) are involved in the synthesis of the copolymers from 0 to 20 mol%.
  • the copolymerization takes place in inert organic solvents which practically do not interfere with the polymerization and which do not react with the monomers.
  • solvents are, for example, C 3 bis
  • Cio-ketones such as acetone, diethyl ketone, methylethyl lketon and cyclohexanone, ethers such as tetrahydrofuran and dioxane, esters of saturated C 2 - to C 4 -carboxylic acids and saturated monohydric C 1 - to C 4 alcohols such as methyl acetate, ethyl acetate, isopropyl acetate , Methyl propionate, ethyl propionate, isobutyl propionate, methyl butyrate, Butyrate and Butterkladreisobutylester, aromatic hydrocarbons such as benzene, toluene, xylene and cumene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, cyclohexane, methylcyclohexane, dimethylcyclohe
  • the polymerization is carried out in carbon dioxide, it takes place at temperatures above 31 ° C. in supercritical carbon dioxide.
  • Acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, toluene or xylene are preferably used as solvents.
  • the polymerization can of course also be carried out in mixtures of inert solvents which do not react with the anhydride groups of the monomers or polymers.
  • the copolymerization takes place in the presence of compounds which break down into free radicals under the polymerization conditions.
  • Suitable polymerization initiators are, for example, hydrogen peroxide, organic peroxides and hydroperoxides, peroxydisulfates, redox initiators and starters.
  • the polymerization can also be carried out by exposure to high-energy radiation or by irradiation of the reaction mixture in the presence of a
  • Photoinitiators such as benzoin, can be made.
  • the initiators should preferably have a half-life of ⁇ 3 hours at the chosen polymerization temperatures. If, for example, polymerization is carried out at a low temperature and polymerization is carried out at a higher temperature, it is advisable to work with at least 2 initiators. For example, the following initiators are suitable for the polymerization temperatures mentioned:
  • redox coinitiators such as benzoin or dimethylani 1 in and organically soluble complexes or salts of heavy metals such as copper, cobalt, manganese, iron, nickel, chromium
  • the half-lives of the peroxides mentioned, especially the hydroperoxides can be reduced , so that, for example, tert-butyl hydroperoxide is effective at 100 ° C. in the presence of 5 ppm copper (II) acety lacetonate.
  • the free radical polymerization initiators are used in conventional amounts, e.g. 0.1 to 5 wt.%, Based on the at
  • Polymerization used amounts of monomers.
  • the copolymerization can optionally be carried out in the presence of customary regulators, for example thio and mercapto compounds such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, thiolactic acid, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan and dodecyl mercaptan.
  • suitable regulators are aldehydes, such as acetaldehyde, propionaldehyde and butyraldehyde and formic acid.
  • the regulators are used in amounts of 0.01 to 2%.
  • the copolymerization can optionally be carried out in the presence of crosslinking agents.
  • Suitable crosslinkers are, for example, ethylene glycol divinyl ether, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate, butanediol-1,4-diacrylate, butane-1,4-dimethacrylate, hexanediol-1, 6-dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate and acrylic acid or methacrylic acid esters of alcohols with more than 2 hydroxyl groups, eg trimethylolpropane triacrylate or trimethylolpropane trimethacrylate.
  • diacrylates and dimethacrylates of polyethylene glycols or polypropylene glycols with molecular weights which are preferably in the range from about 400 to 2000.
  • the di-, trimaleinates and (meth) acrylate maleinates corresponding to the above di- and tri (meth) acrylates can also be used as crosslinkers. If the copolymerization is carried out in the presence of crosslinking agents, then the amount of crosslinker is 0.1 to 2.5% by weight, based on the total monomers used in the copolymerization.
  • the polymerization is preferably carried out in stirred tanks, which are equipped, for example, with an anchor, blade or impeller stirrer.
  • the copolymerization can be carried out, for example, as a solution, precipitation or suspension polymerization.
  • Suitable protective colloids are, for example, copolymers of maleic anhydride with vinyl alkyl ethers which contain 1 to 20 carbon atoms in the alkyl group, or copolymers of maleic anhydride and olefins with 8 to 20 carbon atoms and their monoesters with C 11 -C 20 alcohols or monoamides with C 10 bis C 20 amines.
  • polyalkyl vinyl ethers whose alkyl group contains 1 to 20 carbon atoms, for example polymethyl, polyethyl and polyisobutyl vinyl ether.
  • a protective colloid is used in the copolymerization, the effective amounts are 0.05 to 4% by weight, based on the monomers to be polymerized.
  • the concentration of the monomers in the inert organic solvents is 5 to 70, preferably 15 to 50% by weight.
  • the polymerization temperature is in the range from 40 to 160, preferably 50 to 150 ° C. After the copolymerization has ended, the copolymers can be isolated, for example by distilling off the solvent used in the polymerization or by precipitating the polymers with a suitable solvent.
  • copolymers then remain as a powdery residue. Since the copolymers contain reactive groups such as anhydride and ⁇ -lactone groups, they are sensitive to moisture. When they are brought into contact with water, they hydrolyze easily, two carboxyl groups being formed from each anhydride group and the ⁇ -lactone unit contained in the copolymer reacting with water according to the following reaction scheme
  • the reactive groups in the copolymer in particular the anhydride and ⁇ -lactone groups, can not only be hydrolyzed with water, but can also be reacted with alcohols, primary or secondary amines.
  • Hydrolysis ie the action of water on the copolymer produced, gives rise to water-soluble copolymers which are water-soluble at least in the form of the alkali metal and ammonium salts.
  • the anhydride and ⁇ -lactone groups of the copolymers can be reacted in the organic solvent in which the copolymerization was carried out or the solvents used are first distilled off and then the hydrolysis of the ketene and anhydride groups or their reaction with alcohols or amines is carried out by. The one in hydrolysis
  • Copolymers can be used directly as detergent additives.
  • copolymers in the form of the free acids are not sufficiently soluble in water, they can be used in partially or completely neutralized form. For partial or
  • copolymers preferably sodium hydroxide solution, potassium hydroxide solution, ammonia or alkanolamines, e.g. Ethanolamine, diethanolamine, triethanolamine or mixtures of the bases mentioned.
  • the copolymers are water-soluble, at least in neutralized form and, in the hydrolyzed form, have K values of 15 to 120, preferably 20 to 80 (determined in aqueous solution at pH 7 on the sodium salt of the
  • the non-hydrolyzed copolymers can also be partially esterified by reaction with alcohols, a carboxyl and an ester group being formed from an anhydride group in the polymer in the reaction with an alcohol, and a ⁇ -hydroxycarboxylic acid ester being formed from a ⁇ -lactone unit in the copolymer.
  • Suitable alcohols are, for example, C 1 -C 30 -alcohols or, particularly advantageously, those compounds containing OH groups which are obtained by reacting
  • Suitable compounds (A) are C 1 to C 30 alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, cyclohexanol, n-hexanol, n-octanol, 2 -Ethylhexanol, decanol, dodecanol and stearyl alcohol.
  • the alcohols produced by the oxo process for example C 10 alcohols, are of particular technical importance.
  • C 13 alcohols and C 13 / C 15 alcohols or also native alcohols such as, for example
  • Suitable compounds (A) are also C 8 to C 22 fatty acids, for example
  • component (A) Stearic acid, palmitic acid, coconut fatty acid, tallow fatty acid and lauric acid.
  • C 1 -C 12 -alkylphenols for example n-decylphenol, n-nonylphenol, isononylphenol, n-octylphenol, isobutylphenol and methylphenol.
  • Secondary C 2 - to C 30 -amines are also used as component (A), for example dimethylamine, di-n-butylamine, di-n-octylamine and di-stearylamine.
  • Secondary C 8 to C 18 fatty amines are preferably used.
  • Preferred as component (A) are C 1 - bis
  • Suitable components (B) are C 2 -C 4 -alkylene oxides, for example ethylene oxide, propylene oxide, n-butylene oxide and isobutylene oxide. Tetrahydrofuran can also be used as component (B). Preferred for use
  • Copolymer more than 5, for example 5.5 to 50, preferably 9 to 30% of the total carboxyl groups present are esterified.
  • the esterification itself is generally carried out at higher temperatures, for example 50 to 200, preferably 80 to 150 ° C. in the presence of conventional esterification catalysts.
  • P-Toluenesulfonic acid is particularly suitable as a catalyst.
  • the esterification reaction is after about 0.5 to 20, preferably 1 to 10 hours ended.
  • the partial esterification of the unhydrolyzed copolymers with the reaction products from (A) and (B) leads to products which allow the production of particularly stable storage liquid detergent formulations. Such products are also obtained if the reaction of the non-hydrolyzed copolymers is carried out with long-chain primary amines, for example C 10 -C 22 -alkylamines or amines of the
  • R 1 C 8 - to C 28 -Alky
  • R C 1 to C 28 alkyl, H
  • R 3 , R 4 H, CH 3 , C 2 H 5 ,
  • n 2 to 100
  • R 2 is H or R 1 .
  • the anhydride groups of the copolymers are converted into the corresponding half-amide groups, and ⁇ -hydroxycarboxamides are formed from the ketene groups. Since the non-hydrolyzed copolymers, which contain units of compounds of groups (a), (b) and (c) in copolymerized form as essential constituents, are only partially reacted with alcohols or amines, the anhydride components still present in the copolymer after the reaction are hydrolyzed. and ketene groups. The copolymers thus obtainable can then be partially or completely neutralized with the bases specified above. The hydrolysis can of course also be carried out with the aid of aqueous bases, for example aqueous sodium hydroxide solution.
  • aqueous bases for example aqueous sodium hydroxide solution.
  • the copolymers When the copolymers are neutralized, yellow or orange colored products are obtained with a high proportion of diketene in the polymer. Complete decolorization is achieved by post-treatment with an oxidizing agent, preferably hydrogen peroxide, using 1 to 30 mol% of the oxidizing agent, preferably 2 to 15 mol% hydrogen peroxide become.
  • the oxidizing agent can be added during the neutralization or afterwards at temperatures between 10 and 120 ° C., preferably between 50 and 100 ° C.
  • the copolymers can be used either in the non-hydrolyzed form or in the form of the aqueous solution or in the form of a powder.
  • the starting point is preferably aqueous solutions of the copolymers. Such solutions can of course also for
  • the liquid detergents and the powder detergent formulations each contain 0 to 15, preferably 0.5 to 10% by weight of at least one copolymer of the composition described above.
  • the detergent formulations contain essential components
  • Water-based and water-free liquid detergents can be used, which can be clear or cloudy. If the polymers according to the invention are insoluble in the liquid detergent formulation, the copolymers can also be finely divided and, if necessary, stabilized with dispersants. Suitable anionic surfactants in liquid detergents are, for example, sodium alkylbenzenesulfonates, fatty alcohol sulfates and fatty alcohol polyglycol ether sulfates.
  • Individual compounds of this type are, for example, C 8 - to C 12 -alkylbenzenesulfonates, C 12 - to C 16 -alkanesulfonates, C 12 - to C 16 -alkyl sulfates, C 12 - to C 16 -alkylsulfosuccinates and sulfated ethoxylated C 12 - bis C 16 alkanols.
  • Also suitable as anionic surfactants are sulfated fatty acid alkanolamines, fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.
  • anionic surfactants are fatty acid esters or fatty acid amides of hydroxy or amino carboxylic acids or sulfonic acids, such as, for example, the fatty acid sarcosides, glycolates, lactates, taurides or isothionates.
  • the anionic surfactants can be present in the form of the sodium, potassium and ammonium salts and as soluble salts, organic bases, such as mono-, di- or triethanolamine or other substituted amines.
  • the anionic surfactants also include the usual soaps, ie the alkali salts of the natural fatty acids.
  • Addition products of 3 to 40, preferably 4 to 20 moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkane sulfonamide can be used, for example, as nonionic surfactants (nonionics).
  • nonionic surfactants nonionics
  • the addition products of 5 to 16 moles of ethylene oxide with coconut or tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in are particularly important the alkyl residues.
  • water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • non-ionic surfactants that can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol ether, alkylene diaminopolypropylene glycol and alkyl polypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol ether chain functions as a hydrophobic residue.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants. A reduction can also be achieved by adding non-surfactant-like organic substances.
  • the liquid, aqueous detergents contain 4 to 50% by weight of surfactants. You can contain an anionic or nonionic surfactant in the amount specified. However, it is also possible to use mixtures of anionic and nonionic surfactants. In such a case, the content of anionic surfactants in the liquid detergent is selected from 0 to 50% by weight and the content of nonionic surfactants in the liquid detergent from 0 to 50% by weight, based on the total detergent formulation.
  • the liquid detergents can contain water in amounts of 10 to 60, preferably 20 to 50,% by weight. But they can also be anhydrous.
  • the liquid detergents may also contain other substances for modification. These include, for example, alcohols, such as ethanol, n-propanol and isopropanol, and low molecular weight polyalkylene oxides, such as di-, tri- and tetraethylene glycol or corresponding propylene glycols. If they are used, these substances are used in amounts of 0.1 to 15% by weight, based on the total detergent formulation. used.
  • Anhydrous liquid detergents can also contain peroxy compounds for bleaching in suspended or dispersed form. The following may be mentioned as peroxo compounds: sodium perborate, perosocarboxylic acids and polymers with partially peroxo-containing groups.
  • the liquid detergents may also contain hydrotropes.
  • Complexing agents are, for example, ethylenediaminetetraacetic acid, nitrilotriacetate and isoserinediacetic acid, and phosphates, such as aminotrismethylenephosphonic acid, hydroxyethanephosphonic acid, ethylenediaminetetraethylenephosphonic acid and their salts.
  • the complexing agents are used in amounts of 0 to 10% by weight, based on the detergents.
  • the detergents can also contain citrates, di- or triethanolamine, opacifiers, optical brighteners, enzymes, perfume oils and dyes. If these substances are used to modify the liquid detergents, they are present together in amounts of up to 5% by weight.
  • the detergents are preferably phosphate-free. However, they can also contain phosphates, for example pentasodium triphosphate and / or tetrakai iumpyrophosphate. If phosphates are used, the proportion of the phosphates in the total formulation of the detergent is 10 to 25% by weight. Powder detergents can have different compositions.
  • the registered compounds can also be combined with other known detergent additives (such as incrustation inhibitors, graying inhibitors, clay dispersants and substances that enhance the primary washing action, color transfer inhibitors, bleach activators) in powder and
  • detergent additives such as incrustation inhibitors, graying inhibitors, clay dispersants and substances that enhance the primary washing action, color transfer inhibitors, bleach activators
  • Liquid detergents (phosphate-free and phosphate-free) produce synergistic effects in which not only the incrustation inhibition but also the effect of the other detergent additive can be enhanced.
  • Detergent additives are to be understood here as meaning substances which are used in amounts of up to 15% by weight, based on the detergent formulation, and which have one or more advantageous washing properties.
  • Universal household detergents for drum washing machines usually contain 5 to 10% by weight of anionic surfactants; 1 to 5% by weight of nonionic surfactants; 1 to 5% by weight of foam regulators, such as silicone oils or soaps; 0 to 40 wt .-% softening agents such as soda or Pentasodium triphosphate, which can be partially or completely replaced by the compounds according to the invention; 0 to 30% by weight of ion exchangers, such as zeolite, bentonites, such as, for example, ZeoLith A; 2 to 7% by weight sodium silicates as corrosion inhibitors; 10 to 30% by weight of bleaching agents, such as sodium perborate or sodium percarbonate; 0 to 5 wt .-% bleach activators, such as
  • Tetraacetylethylene diamine pentaacetyl glucose, hexaacetyl sorbitol or acyloxybenzenesulfonate; Stabilizers, such as magnesium silicate or ethylenediaminetetraacetate; Graying inhibitors, such as carboxymethyl cellulose, methyl and hydroxyalkyl celluloses, polyglycols grafted with vinyl acetate, oligomeric and polymeric terephthalic acid / ethylene glycol / polyethylene glycol esters; Enzymes; optical brighteners; Fragrances; Dyes and fillers.
  • the percentages in the examples are% by weight.
  • the K values of the hydrolyzed copolymers were measured in aqueous solution at 25 ° C., a pH of 7.0 and a polymer concentration of 2% by weight of the sodium salts of the copolymers. Examples 1 to 5
  • the reaction mixture is stirred for a further 3 hours at 80 ° C., then 300 g of water are added and the mixture is adjusted to a pH of 6.5 while cooling with 150 g of a 50% strength aqueous sodium hydroxide solution.
  • the copolymers are then each precipitated by adding a mixture of acetone and methanol in a weight ratio of 1: 1 and dried at 75 ° C. in vacuo.
  • the products are colored yellow and have the K values given in Table 1. Examples 6 to 8
  • Amounts of diketene given in Table 1, which is dissolved in 50 ml of toluene, and acrylic acid are added in each case.
  • a solution of 4.2 g of tert-butyl perpivalate (75% in al-ipatic hydrocarbons) in 50 ml of toluene is added to the reaction mixture within 2.5 hours.
  • the reaction mixture is stirred for a further 3 hours at 80 ° C., then 300 g of water are added and, with cooling, 150 g of a 50% strength aqueous solution
  • the reaction mixture is stirred at 80 ° C. for a further 2 hours.
  • the solvent is then distilled off in vacuo and the copolymer is hydrolyzed by adding aqueous sodium hydroxide solution and adjusted to a pH of 7.
  • a mixture of acetone and methanol in a weight ratio of 1: 1 is added to the aqueous solution, so that the salt of the copolymer precipitates.
  • the K value of the copolymer is 24.5 under the conditions specified above.
  • Acrylic acid uses 0.7 moles of methacrylic acid. A copolymer with a K value of 26.9 is obtained.
  • Example 11 Example 4 is repeated with the exception that 40 mol% of the
  • Example 5 is repeated, the neutralization by adding
  • Example 12 was repeated with the exception that 29 g of hydrogen peroxide (30% strength) were metered in during the neutralization.
  • the polysodium salt of the copolymer obtained was colorless and had a K value of 28.5.
  • Example 14 Example 12 was repeated with the exception that 58 g of 30% hydrogen peroxide were used during the neutralization.
  • the polysodium salt of the copolymer obtained was colorless and had a K value of 26.2.
  • the copolymers described above were each incorporated into two different powder detergents A and B. Test fabrics made of cotton and cotton terry cloth were washed with these detergent formulations. The number of wash cycles was 15. After this number of washes, the ash content of the fabric was determined by ashing the test fabric in each case. The ash content is given in% by weight. The more effective the copolymer contained in the detergent, the lower the ash content of the test fabric.
  • wash liquor 250 g, the water used has 4 mmol hardness per liter (molar ratio:

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Abstract

Copolymères contenant sous forme polymérisée en tant que monomères caractéristiques (a) entre 10 et 60 % en moles d'anhydrides d'acide biccarbonique monoéthyléniquement insaturés avec 4 à 8 atomes de C; (b) entre 5 et 60 % en moles de dicétène; et (c) entre 0,5 et 60 % en moles d'au moins un acide monocarbonique monoéthyléniquement insaturé avec entre 3 et 8 atomes de C. Ces copolymères, sous leur forme hydrolisée, ont des valeurs K comprises entre 15 et 120 (selon la méthode de H. Fikentscher, dans une solution aqueuse à 25°C, avec un pH de 7, la concentration du sel de sodium dans les copolymères étant de 2 % en poids). L'invention porte en outre sur un procédé de fabrication des copolymères qui consiste à polymériser des monomères des groupes (a), (b) et (c) dans des solvants inertes, en présence d'excitants de polymérisation, à des températures relativement élevées, et à isoler les copolymères ou, le cas échéant, à les soumettre à une solvolyse. Ces copolymères peuvent être utilisés en tant qu'additifs dans des détergents liquides ou en poudre, à raison de 0,1 à 15 % en poids.
EP90906186A 1989-04-21 1990-04-19 Copolymeres a base d'anhydrides d'acide bicarbonique monoethyleniquement insatures, de dicetene et d'acides monocarboniques monoethyleniquement insatures; production et utilisation de ces copolymeres Withdrawn EP0469018A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3913127 1989-04-21
DE3913127A DE3913127A1 (de) 1989-04-21 1989-04-21 Copolymerisate auf basis von monoethylenisch ungesaettigten dicarbonsaeureanhydriden, diketen und monoethylenisch ungesaettigten monocarbonsaeuren, ihre herstellung und verwendung

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EP0469018A1 true EP0469018A1 (fr) 1992-02-05

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EP90906186A Withdrawn EP0469018A1 (fr) 1989-04-21 1990-04-19 Copolymeres a base d'anhydrides d'acide bicarbonique monoethyleniquement insatures, de dicetene et d'acides monocarboniques monoethyleniquement insatures; production et utilisation de ces copolymeres

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ATE124057T1 (de) * 1990-12-06 1995-07-15 Hoechst Celanese Corp Verfahren zur herstellung von 4- hydroxystyrolpolymeren aus 4- acetoxystyrolpolymeren.
DE4410196A1 (de) * 1994-03-24 1995-09-28 Basf Ag Als Paraffindispergatoren geeignete modifizierte Copolymerisate, ihre Herstellung und Verwendung sowie diese enthaltende Erdölmitteldestillate
DE4410198A1 (de) * 1994-03-24 1995-09-28 Basf Ag Copolymerisate auf Basis von Diketenen, ethylenisch ungesättigten Dicarbonsäuren bzw. Dicarbonsäurederivaten und ethylenisch ungesättigten Kohlenwasserstoffen
DE19719689A1 (de) 1997-05-09 1998-11-12 Basf Ag Fließverbesserer für Erdölmitteldestillate
WO2012065120A2 (fr) 2010-11-11 2012-05-18 Segetis, Inc. Polymères ioniques, procédé de fabrication et leurs utilisations

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JPS5039791A (fr) * 1972-08-31 1975-04-12
CH584725A5 (fr) * 1974-07-16 1977-02-15 Ciba Geigy Ag
DE2936984A1 (de) * 1979-09-13 1981-04-02 Basf Ag, 6700 Ludwigshafen Verwendung von (meth)acrylsaeure-maleinsaeure-copolymerisaten als inkrustierungsinhibitoren in waschmitteln

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See references of WO9012821A1 *

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WO1990012821A1 (fr) 1990-11-01
DE3913127A1 (de) 1990-10-25

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