WO1992002606A1 - Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage - Google Patents

Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage Download PDF

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WO1992002606A1
WO1992002606A1 PCT/EP1991/001360 EP9101360W WO9202606A1 WO 1992002606 A1 WO1992002606 A1 WO 1992002606A1 EP 9101360 W EP9101360 W EP 9101360W WO 9202606 A1 WO9202606 A1 WO 9202606A1
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carboxylic acids
monoethylenically unsaturated
polymer
polymers
acid
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German (de)
English (en)
Inventor
Matthias Kroner
Fritz Erdmann Kempter
Richard Baur
Paul Diessel
Volker Schwendemann
Walter Denzinger
Heinrich Hartmann
Manfred Niessner
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BASF SE
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BASF SE
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Priority to DE59103296T priority Critical patent/DE59103296D1/de
Priority to EP91912925A priority patent/EP0541588B1/fr
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    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the invention relates to the use of polymers which as
  • EP-PS 0 025 551 are described. This involves the use of copolymers of maleic acid and acrylic acid as an incrustation inhibitor in detergents. These copolymers are used in amounts of up to 10% by weight in the detergent formulation. With the aid of these copolymers, it is possible to replace all or part of the phosphates previously used in detergents. After the washing process, the copolymers end up in the wastewater and are almost completely absorbed in sewage treatment plants. In the case of liquid detergents which contain copolymers of acrylic acid and maleic acid as a phosphate substitute, however, segregation often occurs during storage.
  • EP-PS 1 116 930 discloses water-soluble copolymers from 40 to
  • Unsaturated dicarboxylic acid with 4 to 8 carbon atoms and / or their corresponding dicarboxylic acid anhydrides in which 2 to 60% by weight, based on the total weight of the carboxylic acids or carboxylic acid anhydrides, with alkoxylated C 1 -C 18 -alcohols or C 1 - Until C 12 alkylphenols are esterified.
  • the partially esterified copolymers and their water-soluble salts are used, inter alia, in amounts of 0.5 to 10% by weight in liquid detergent formulations.
  • the compatibility of the partially esterified copolymers of at least one monoethylenically unsaturated mono- carboxylic acid and at least one monoethylenically unsaturated dicarboxylic acid are significantly cheaper than in the non-esterified products, so that there is less phase separation.
  • the partially esterified copolymers of the type described are not stable to hydrolysis, so that they hydrolyze in liquid detergent formulations. As a result, inhomogeneities occur, which can even go so far as to result in the phase separation of the liquid detergent.
  • EP-A-0 237 075 discloses liquid detergents which contain at least one non-ionic surface-active agent in an amount of 5 to
  • liquid alkaline detergent formulations which, in addition to water and detergents as stabilizers, contain 0.1 to 5%, based on the entire formulation, of a hydrolyzed copolymer of an ⁇ , ⁇ -unsaturated carboxylic acid anhydride with a vinyl ester,
  • the alcohol components used for esterification include addition products of alkylene oxides, in particular ethylene oxide onto alkylphenols, also come into consideration.
  • EP-A-0 215 251 describes the use of homopolymers
  • Acrylic acid and methacrylic acid copolymers of acrylic acid and methacrylic acid as well as copolymers of ethylenically unsaturated dicarboxylic acids with 4 to 6 carbon atoms and acrylic acid or methacrylic acid in each case with long-chain amines partially neutralized and / or partially amidated form as a graying-inhibiting additive to detergents and cleaning agents which promote the primary washing action known in amounts of 0.05 to 10 wt .-%.
  • Homopolymers and copolymers are produced by reacting the polymers with long-chain amines. In many cases they still contain free amines, which are undesirable in detergent formulations because of their smell and physiological concern. Furthermore, copolymers of acrylic acid and methacrylic acid esters of ethoxylated alcohols as addition of detergents are known from US Pat. No. 4,797,223.
  • EP-A-0 368 214 describes the use of copolymers of monoethylenically unsaturated C 3 to C 8 carboxylic acids, esters of these carboxylic acids with alkyl vinyl ethers or mixtures of these monomers and amides of monoethylenically unsaturated C 3 to C 8 carboxylic acids where the amide groups contain a C 8 -C 28 -alkyl radical or a polyalkyleneoxy radical which is bonded to the nitrogen atom via an alkylene group, as an additive to liquid detergents in amounts of up to 20% by weight.
  • Such copolymers indeed allow the production of liquid detergents that are stable in storage, but they hydrolyze relatively quickly at the high pH values of the detergent formulations.
  • the present invention is based on the object of providing other polymers which are easy to prepare and hydrolysis-stable at high pH values for use in detergents and cleaning agents.
  • polymers which, as essential monomers, contain at least 5% by weight of N- (alkyloxypolyalkoxymethyl) carbonamides of monoethylenically unsaturated C 3 - bis
  • R 1 C 1 to C 28 alkyl, C 3 to C 28 alkenyl, phenyl and C 1 to
  • R 2 , R 3 H, CH 3 , C 2 H 5 ,
  • n 1 to 200
  • polymerized contain, as an additive to low-phosphate and phosphate-free detergents and cleaning agents in amounts that increase the primary and secondary washing ability of these agents.
  • Those to be used in washing and cleaning agents according to the invention are, as an additive to low-phosphate and phosphate-free detergents and cleaning agents in amounts that increase the primary and secondary washing ability of these agents.
  • polymers contain at least 5% by weight of N- (alkyloxy-polyalkoxymethyl) carboxamides monoethylenically
  • R 1 C 1 to C 28 alkyl, C 3 to C 28 alkenyl
  • m 1 to 100, preferably 3 to 70.
  • R 1 C 1 to C 28 alkyl
  • C 3 is C 28 alkenyl, phenyl and
  • R 2 , R 3 H, CH 3 , C 2 H 5 and
  • n 1 to 200, preferably 3 to 100.
  • alkylphenols with alkylene oxides with 2-4 carbon atoms The compounds containing OH groups mentioned can be reacted, for example, with ethylene oxide, propylene oxide or butylene oxide.
  • the alkylene oxides can be used either alone or as a mixture in the alkoxylation. be set. In the latter case, alkoxylation gives rise to products which contain the alkylene oxides copolymerized in a random distribution. However, the alkylene oxides can also be used in succession in the alkoxylation reaction, so that block copolymers are formed.
  • a compound of the general formula R 1 -OH in which R 1 has the meaning given in formula III, is first reacted with ethylene oxide, then with propylene oxide and then with butylene oxide.
  • R 1 has the meaning given in formula III
  • Ethylene oxide and / or propylene oxide are preferably used as alkoxylating agents. They are preferably used in an amount of 3 to 100 mol / mol alcohol.
  • the compounds of formula III are preferably water-soluble.
  • the carboxylic acids on which the amides with structure I are based are, for example, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, citraconic acid, crotonic acid, fumaric acid, itaconic acid and vinyl acetic acid.
  • Preferred monomers for the preparation of the polymers to be used according to the invention are derived from acrylamide and methacrylamide in which the amide groups have the structure I.
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 7 -OC 13/15 alkyl
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 3 -OC 13/15 alkyl
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 11 -OC 13/15 alkyl
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 30 -OC 13/15 alkyl
  • CH 2 C (CH 3 ) -CO-NH-CH 2 - (O-CH 2 -CH 2 ) 7 -OC 13/15 alkyl
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 25 -OC 16/18 alkyl
  • amide groups of structure I monomers are either sown alone to homopolymer or polymerized with one another to form copolymers. According to the invention, these polymers are used as additives for detergents and cleaners, as are copolymers of the carbonamide groups of structure I with other ethylenically unsaturated monomers.
  • copolymers are considered a) 10 to 99 wt .-% of N- (alkyloxy-polyalkoxymethyl) carbonamides monoethylenically unsaturated C 3 - to C 8 -carboxylic acids with amide groups of structure I and
  • Suitable monomers of group b) are, for example, monoethylenically unsaturated C 3 to C 8 carboxylic acids, their esters with C 1 to C 28 alcohols, esters of monoethylenically unsaturated C 3 to C 8 carboxylic acids with reaction products of C 1 to C 28 alcohols and ethylene oxide, propylene oxide and / or butylene oxide in a molar ratio of 1: 1 to 1: 100, amides, NC 1 to C 18 alkyloxymethylamides and nitriles of monoethylenically unsaturated C 3 bis
  • C 8 carboxylic acids vinyl esters of saturated carboxylic acids having 1 to 20 C atoms, C 1 to C 28 alkyl vinyl ether, styrene or mixtures thereof.
  • Suitable monoethylenically unsaturated C 3 to C 8 carboxylic acids are, for example, acrylic acid, methacrylic acid, vinyl acetic acid, 2-ethyl acrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid. acrylic acid, methacrylic acid and maleic acid are preferred.
  • Suitable esters of the aforementioned carboxylic acids with C 1 - to C 28 alcohols are, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl lacrylat, isopropyl, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate , the corresponding butyl esters of methacrylic acid, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, isobutyl acrylate, isobutyl methacrylate, palmitylacrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, maleate dimethyl ester, maleinsate maleate maleate maleate butyl ester
  • polymers which, as comonomers of group b), contain esters of monoethylenically unsaturated C 3 -C 8 -carboxylic acids and polyhydric alcohols in copolymerized form, for example hydroxylethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl acid and acrylate, and methacrylate, and the esters Maleic acid of 1,6-hexanediol.
  • Suitable esters of monoethylenically unsaturated C 3 to C 8 carboxylic acids with reaction products from alcohols and alkylene oxides are, for example, the esters of acrylic acid and methacrylic acid with ethoxylated C 1 to C 28 alcohols, which are formed by addition of 1 to 100 mol of ethylene oxide onto 1 Moles of a monohydric or polyhydric alcohol are formed.
  • mixtures of alkylene oxides can also be used, for example mixtures of ethylene oxide, propylene oxide and / or butylene oxide. In this case, statistical additions of the alkylene oxides to the alcohols are obtained. Further variations are possible by first adding ethylene oxide to the alcohols, for example, and then
  • Propylene oxide and / or butylene oxide or the order of addition of the alkylene oxides to the alcohols changes.
  • Such a stepwise addition of alkylene oxides to alcohols gives alkoxylated alcohols which contain the added alkylene oxides in copolymerized form in the form of blocks.
  • esters of acrylic acid or methacrylic acid come into consideration, but also the esters of the other carboxylic acids mentioned above, e.g. the maleic, fumaric and itaconic esters of the add-on products. Both the mono- and the diesters of the dibasic carboxylic acids come into consideration.
  • Suitable monomers of group b) are C 1 to C 28 alkyl vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether.
  • Styrene can also be used as the monomer of group b). of the amides and nitriles of monoethylenically unsaturated C 3 to
  • C 8 carboxylic acids are especially acrylamide, methacrylamide, acrylonitrile and methacrylonitrile.
  • N-Alkyloxymethyl-carboxamides with C 1 - to C 18 -alkyl radicals serve as starting products for the preparation of the monomers a) by reaction with alkoxylated alcohols and as a monomer of group b).
  • starting products are: N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, N-propoxymethylacrylamide, N-propoxymethyl-methacrylamide, N-iso-propoxymethylacrylamide, N-iso-methacrylamide, N-iso-methacrylamide N-Btuoxymethyl methacrylamide, N-iso-butoxymethylacrylamide, N-iso-butoxymethyl methacrylamide, N-tert-butoxymethylacrylamide, N-tert-butoxymethyl methacrylamide, as well as higher homologues such as N-decyloxymethylacrylamide, N-decyloxymethyl-methadyl methacryl
  • N-alkoxymethyl carboxamides N-butoxymethylacrylamide, N-butoxymethyl methacrylamide, N-iso-butoxymethylacrylamide and
  • N-iso-butoxymethyl methacrylamide is preferably used.
  • Suitable vinyl esters of saturated carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and vinyl stearate.
  • Suitable monomers of group b) are: N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl formamide, N-vinyl acetamide and monomers containing sulfo groups, such as acrylamidopropanesulfonic acid, allylsulfonic acid, vinyl sulfonic acid and their alkali metal and ammonium salts.
  • the monomers of group b) can be used either alone or in the form of mixtures in the preparation of the polymers.
  • the polymers can, for example, contain copolymerized acrylic acid and maleic acid or methacrylic acid and maleic acid as a monomer of group b).
  • monomer combinations that may be considered are, for example, acrylic acid and vinyl acetate, acrylic acid and vinyl propionate, acrylic acid and ethyl acrylate, acrylic acid and ethyl methacrylate, acrylic acid and methyl acrylate, acrylic acid and methyl methacrylate, and also acrylic acid and N-butoxymethylacrylamide, acrylic acid and N-butoxymethyacrylamide, acrylic acid and n-butoxymethyl acrylamide -Butoxymethylacrylamid, acrylic acid and N-iso-Butoxymethy Imethacrylamid as well as acrylic acid and vinyl propionate.
  • the monomers of group b) are preferably 1 to 90% by weight involved in the construction of the copolymers.
  • the polymers can optionally contain, as group c), polymerized monomers having at least two ethylenically unsaturated double bonds.
  • suitable chain extenders are, for example, diacrylates or dimethacrylates of at least dihydric saturated alcohols, for example ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate, butanediol-1,4-dimethacrylate , Hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacryiate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol methacrylate.
  • Acrylic acid and methacrylic acid esters of alcohols with more than two hydroxyl groups are also suitable chain extenders, for example Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate.
  • Another class of chain extenders are the acrylates and the methacrylates of polyethylene glycols or polypropylene glycols with molecular weights which are preferably in the range from 400 to 2000 each.
  • block copolymers of ethylene oxide and propylene oxide or static copolymers of ethylene oxide and propylene oxide are also suitable, each of which is esterified in the ⁇ , ⁇ position with acrylic acid, methacrylic acid, maleic acid or itaconic acid.
  • Chain extenders of this type are, for example, esters of glycols with maleic acid in a molar ratio of 1: 2, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate and also the diacrylates or dimethacrylate of a polyethylene glycol group of polyethylene glycols ethylenically unsaturated C 3 - to C 6 -carboxylic acids, for example vinyl acrylate, vinyl methacrylate or vinyl itaconate.
  • Vinyl esters of at least are also suitable
  • Saturated carboxylic acids containing 2 carboxyl groups and the di- and polyvinyl ethers of at least dihydric alcohols e.g. Adipic acid divinyl ester, butanediol divinyl ether and trimethylol propane trivinyl ether.
  • Other monomers of group c) are, for example, allyl esters of ethylenically unsaturated carboxylic acids, e.g. Allyl acrylate and allyl ether, triallyl sucrose and pentaallyl sucrose.
  • Methylenebisacrylamide, methylenebismethacrylamide and N-divinylethyleneurea, divinylbenzene, divinyldioxane, tetraallylsilane and tetravinylsilane are also monomers of the
  • Group c) suitable- If the monomers of group c) are used in the preparation of the polymers, they are present in the polymers in amounts of from 0.01 to 20, preferably 0.05 to 10,% by weight in polymerized form.
  • the monomers of group c) can be used either alone or as a mixture with one another.
  • the polymers to be used according to the invention can be obtained by polymerizing the monomers a) alone or in a mixture with at least one monomer from group b) and / or from group c). They can be produced by all common polymerization processes, e.g. by
  • the copolymers are preferably obtained by solution polymerization. In all polymerization processes, the initiators which break down into free radicals under polymerization conditions are used. The polymerization temperatures are in the range from 20 to 200, preferably 30 to 150 ° C.
  • the mono- and dicarboxylic acids of the monomers of group b) can be used both as free carboxylic acids, in partially or completely neutralized form in the copolymerization. The degree of neutralization - especially when using dicarboxylic acids as the monomer of group b) - can have a considerable influence on the course of the polymerization, for example conversion, speed, molecular weight and residual monomer content in the copolymer.
  • inorganic or organic bases can be used, for example sodium hydroxide solution, potassium hydroxide solution, ammonia, amines, such as dimethylamine, triethanolamine, triethylamine, trimethylamine, tributylamine, ethanolamine or diethanolamine. Mixtures of different bases can also be used for neutralization, for example mixtures of sodium hydroxide solution and triethanolamine.
  • the monomers from group b) containing acid groups are preferably used in neutralized form.
  • the pH of the aqueous monomer solution is preferably above 6.5, for example in the range from 7 to 11 or even above.
  • the non-neutralized carboxylic acid can also be used in anhydrous media. All known radical donors can be used as initiators. These initiators can be soluble or insoluble in water. Water-soluble initiators are, for example, inorganic peroxides, such as potassium, sodium and ammonium peroxodisulfate and hydrogen peroxide. Organic peroxides, hydroperoxides, peracids, ketone peroxides, perketals and peresters, for example, are also suitable as initiators
  • Suitable reducing components are, for example, cerium III and iron II salts, sodium sulfite, sodium
  • Suitable initiators are preferably selected by using compounds which form free radicals and which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If the polymerization is first started at a lower temperature and ends at a higher temperature, it is advisable to work with at least two initiators which decompose at different temperatures, namely first an initiator which already decomposes at a lower temperature for the start of the polymerization and then the Complete the main polymerization with an initiator that decomposes at a higher temperature. By adding heavy metal salts, e.g.
  • Suitable initiators are also azo compounds, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2 , 4-dimethylvaleronitrile) and dimethyl-2,2'-azobisisobutyrate.
  • Hydrogen peroxide, potassium, sodium and ammonium peroxodisulfate, tert-butyl perpivalate, 2,2'-azobis (2,4-dimethylvaleronitrile) and di-tert-butyl peroxide are particularly preferably used as initiators in the polymerization.
  • Based on the monomers to be polymerized usually 0.5 to 10, preferably 1 to 8% by weight of an initiator or a mixture of polymerization initiators is used.
  • the amount of initiator used is known to have a considerable influence on the molecular weight of the homopolymers and copolymers formed.
  • the polymerization is preferably carried out in the presence of a diluent. These can be solvents for the monomers and the polymers or only solvents for the monomers.
  • Suitable solvents for solvent polymerization are, for example, aromatic hydrocarbons, such as toluene, xylene, cumene and tetralin, aliphatic hydrocarbons, such as hexane, heptane, octane, cyclohexane and isooctane, and preferably ethers, such as diethyl ether, dibutyl ether, diisobutyl ether, methyl tert-butyl ether , Cyclic ethers, such as tetrahydrofuran and dioxane, mono- or dialkyl ethers of mono- or polyethylene glycols, for example ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethyl glycol dimethyl ether, diethylene glycol dibutyl ether, monoalkyl ethers of mono- or polyethylene glycol acetates, such as methyl glycol acetate, methyl ethylene glyco
  • the molecular weights of these addition products can be up to 8000, preferably up to 6000. If at least 2 different alkylene oxides are used to prepare the addition products, the alkylene oxide units in the reaction products can be randomly distributed or can be in the form of blocks.
  • Such reaction products are components of liquid detergents. Since the polymers are used in detergents, they are advantageously prepared as solvents in the addition products described and the resulting polymer solution can be used directly to prepare the detergent formulation.
  • Preferred solvents for the polymerization are, for example, reaction products of monohydric C 1 to C 28 aliphatic alcohols or C 1 to C 18 alkylphenols with ethylene oxide, propylene oxide and / or butylene oxide, for example the adducts of 3 to 11 moles of ethylene oxide with one mole of one C 13 / C 15 alcohol, adducts of 5 to 15 moles of ethylene oxide with 1 mole of nonylphenol, adducts of 7 to 11 moles of ethylene oxide and 3 to 5 moles of propylene oxide with 1 mole of oleyl alcohol and adducts of 5 to 15 moles of ethylene oxide with 1 mole of stearyl alcohol or Taig fatty alcohol.
  • the addition products of ethylene oxide, propylene oxide and butylene oxide with polyhydric alcohols for example glycol, diethylene glycol, are also suitable.
  • other suitable solvents are C 1 to C 6 alcohols, such as methanol, ethanol, isopropanol, n-propanol, butanols, n-hexanol and cyclohexanol, ketones, for example acetone, ethyl methyl ketone and cyclohexanone, esters, for example
  • Ethyl acetate and water and mixtures of water with water-soluble organic solvents. If an inert solvent is used in the polymerization, the concentrations of the monomers therein are 10 to 90, preferably 15 to 70% by weight.
  • the polymerization of the monomers of groups a) to c) can optionally also be carried out in the presence of regulators.
  • Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, 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, hydroxylammonium sulfate and butenols.
  • Regulators are used in particular when larger amounts of monomers from group c) are used in the polymerization. In such cases, the use of the regulators gives water-soluble polymers or Polymers that are easily dispersible in water. If the polymerization is carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers to be polymerized, are used.
  • the polymerization is carried out in conventional devices which are provided with mixing elements. For example, flasks, kettles, autoclaves and cylindrical reactors equipped with stirrers are suitable.
  • the polymerization can also be carried out in vessels, cascades or in interconnected polymerization devices.
  • Polymerization can be carried out batchwise or continuously. Kneaders are also suitable as the polymerization device. If water-soluble monomers are used in the polymerization, the polymerization can also be carried out by the reverse suspension polymerization method or by the water-in-oil emulsion polymerization method. However, the polymerization is preferably carried out as solution polymerization. The production of polymers by the precipitation polymerization method can be of interest for special applications. In addition to the catalytic action of compounds which decompose into radicals under the polymerization conditions, the polymerization can also be initiated by the action of high-energy radiation, e.g. by UV radiation or by exposure to ⁇ , ⁇ or ⁇ rays.
  • high-energy radiation e.g. by UV radiation or by exposure to ⁇ , ⁇ or ⁇ rays.
  • the polymerization is usually carried out in apparatus designed to be pressure-tight.
  • the polymerization is preferably carried out in the absence of oxygen in an inert gas atmosphere, e.g. under nitrogen, argon, helium or carbon dioxide at normal pressure.
  • the monomers to be polymerized are mixed
  • the monomers can also be introduced into the polymerization reactor in bulk or in the form of a solution.
  • homopolymers or copolymers are obtained which have K values from 8 to 200, preferably 10 to 100.
  • polymerization is carried out in organic solvents, it is expedient to first neutralize the copolymers and only then to convert them into aqueous solutions or dispersions, which are then used as additives in detergents and cleaning agents. If it is necessary to separate off the organic solvents, it can be done, for example, by distillation.
  • N (alkyloxy-polyalkoxymethyl) carboxamides of monoethylenically unsaturated C 3 -C 8 -carboxylic acids with amide groups of structure I are used as an additive to detergents and cleaning agents in order to increase the primary and secondary washability of the detergent and cleaning agent formulations.
  • the detergents and cleaning agents contain essential ones
  • compositions other than the polymers described above which are used in an amount of 0.1 to 20 wt .-%, at least one anionic surfactant, a nonionic surfactant or mixtures thereof.
  • the detergents and cleaning agents can be in the form of a powder or a liquid formulation.
  • the copolymers to be used according to the invention are particularly suitable for the preparation of liquid detergent formulations.
  • Suitable anionic surfactants 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 alkyl sulfosuccinates and sulfated ethoxylated C 12 to C 16 -Alkanols.
  • anionic surfactants are sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.
  • Other suitable 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 organic in the form of the sodium, potassium and ammonium salts and also as soluble salts Bases such as mono-, di- or triethanolamine or other substituted amines are present.
  • 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 alkanesulfonamide can be used, for example, as nonionic surfactants (nonionics).
  • nonionics 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.
  • non-fully or not fully 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 foam capacity of the surfactants can be increased or reduced by combining suitable types of surfactants. A reduction can also be achieved by adding non-surfactant-like organic substances.
  • the liquid, aqueous detergents contain 10 to 50% by weight
  • 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 10 to 30% by weight and the content of nonionic surfactants in the
  • Liquid detergent from 5 to 20 wt .-%, based on the total
  • Liquid detergents contain the essential component according to
  • Copolymers to be used according to the invention in amounts of 0.1 to 20 preferably 1 to 10 wt .-% and optionally water in amounts of 10 to 60, preferably 20 to 50 wt .-%.
  • Liquid detergents may also contain other substances for modification. These include, for example, alcohols, such as ethanol, n-propanol and isopropanol. If used, these substances are used in amounts of 3 to 8% by weight, based on the total detergent formulation.
  • the liquid detergents may also contain hydrotropes. This includes compounds such as 1,2-propanediol, cumene sulfonate and toluene sulfonate. If such compounds are used to modify the liquid detergent, their amount, based on the total weight of the liquid detergent, is 2 to 5% by weight. In many cases, addition of complexing agents has also proven to be advantageous for modification.
  • Complexing agents are, for example, ethylenediaminetetraacetic acid, nitrilotriacetate and isoserinediacetic acid, and phosphonates, such as aminotrismethylenephosphonic acid, hydroxyethane diphosphonic acid, ethylenediaminetetramethylenephosphonic acid and their salts.
  • the complexing agents are used in amounts of 0 to 10% by weight, based on the liquid detergent.
  • the liquid detergents can also contain citrates, di- or triethanolamine, opacifiers, optical brighteners, enzymes, perfume oils and dyes. If they are used to modify the liquid detergents, these substances are present together in amounts of up to 5% by weight.
  • Liquid detergents are preferably free of phosphates. However, they can also contain phosphates, e.g. Pentasodium triphosphate and / or tetrakaiium pyrophosphate. If phosphates are used, the proportion of phosphates in the total formulation of the liquid detergent is 10 to
  • liquid detergents described above have the advantage over the powder detergents that they are easy to dose and have a very good fat and oil dissolving power at greasy soiled laundry at lower washing temperatures.
  • Liquid detergents contain high levels of detergent substances, which remove dirt from the textile fabric at washing temperatures of 40 to 60 ° C.
  • the dispersing properties of polymers have so far not been able to be used in aqueous liquid detergents because they are higher as a result
  • Secondary washing is understood to mean the effects which arise from the re-accumulation of the dirt detached from the fabric on the fabric in the wash liquor.
  • the secondary washing effect can only take place after several washes, e.g. 3, 5, 10 or even 20 washes become visible, which becomes increasingly gray (noticeable), i.e. Accumulation of dirt from the wash liquor on the fabric.
  • standard soiling fabric is washed several times together with white test fabric and the soiled fabric is renewed after each wash.
  • the dirt detached from the dirt fabric, which is drawn onto the white test fabric during washing causes a drop in the degree of whiteness that is measured.
  • the homopolymers and copolymers to be used according to the invention in detergents or their water-soluble salts can also be used for the formulation of powder detergents.
  • composition of powder detergent formulations can vary widely. The same applies to the composition of detergent formulations.
  • Detergent and cleaning agent formulations usually contain surfactants and optionally builders. This information applies to both liquid and powder detergents
  • the percentages in the examples are% by weight.
  • the K values were determined according to H. Fikentscher, Zellulosechemie, Vol. 13, 58-64 and 71-74 (1932).
  • the K values of the water-soluble polymers were measured in aqueous solution at 25 ° C. at a pH of 7.5 and a polymer concentration of 1% by weight.
  • the K values of the water-dispersible polymers were measured as 1% oily solutions in the unneutralized form in tetrahydrofuran (THF) at 25 ° C.
  • the K values determined in this way are in all cases between 8 and 200, preferably between 10 and 100. Examples
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 7-OC 13/15 alkyl
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 3 -OC 13/15 alkyl
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 11 -OC 13/15 alkyl
  • CH 2 CH-CO-NH-CH 2 - (O-CH 2 -CH 2 ) 25-OC 16/18 alkyl
  • tetrahydrofuran 125 g are placed under a nitrogen atmosphere in a 500 ml round-bottomed flask equipped with a stirrer, reflux condenser, nitrogen inlet and feed devices and heated to boiling under reflux.
  • a solution of 37.5 g of acrylic acid in 35 g of tetrahydrofuran, a solution of 37.5 g of acrylamide derivative 1 in 35 g of tetrahydrofuran and a solution of 1 within 2 hours are then simultaneously added to this template from 3 feed vessels within 1 hour. 5 g
  • 2,2'-Azobis (2,4-dimethylvaleronitrile) in 20 g tetrahydrofuran After the initiator addition has ended, the reaction mixture is heated to boiling under reflux for a further 2 hours, cooled to 20 ° C. and neutralized by adding a mixture of 124 g of triethanolamine and 50 g of tetrahydrofuran. The wax-like flask contents are mixed with 300 g of water and the solution obtained is freed from tetrahydrofuran by distillation. A slightly yellowish, clear, aqueous, viscous solution with a solids content of 27% and a K value of 32 (measured in aqueous solution) is obtained.
  • Cyclohexane precipitated The polymer is filtered off and dried in vacuo at 100 ° C. A 35% aqueous solution with a K value of 18 (measured in aqueous solution) is prepared by adding water.
  • aqueous solution of 135 g of acrylic acid in 150 g of water is neutralized with 227 g of 50% strength aqueous potassium hydroxide solution and a solution of 67 g of the acrylamide derivative 1 in 200 g of isopropanol is added.
  • the resulting clear solution is continuously added within 1 hour and at the same time separately a solution of 2 g of mercaptopropionic acid in 20 g of water and 20 g of isopropanol in the polymerization device described in the preparation of polymer 3 and polymerized at a bath temperature of 90 ° C., wherein 6.7 g of 30% aqueous hydrogen peroxide in 30 g of water and 30 g as the polymerization initiator
  • reaction mixture is heated to boiling for a further hour, cooled and then neutralized by adding 67 g of 50% strength aqueous sodium hydroxide solution and 400 g of water.
  • aqueous sodium hydroxide solution is then distilled off and the solids content of the aqueous solution is then adjusted to 15% by adding water.
  • the 15% aqueous solution has a viscosity of 1062 mPas at a temperature of 20 ° C.
  • the K value is 25.6 (measured in aqueous solution).
  • Polymers 6 to 12 are prepared in accordance with the process specification given above using the starting materials shown in Table 1.
  • the procedure is as described for the preparation of polymer 14, except that 50 g of acrylamide derivative 3, 40 g of vinyl acetate and 10 g of acrylic acid in 100 g of tetrahydrofuran are polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran. After the polymerization, 11 g of 50% strength are added aqueous sodium hydroxide solution in 200 g of water. After distillation and dilution of the mixture with water, a 30% strongly cloudy polymer solution with a viscosity of 12833 mPas is obtained. The K value of the polymer in the unneutralized form is 20.3 (determined on solutions of the polymer in THF).
  • reaction mixture is heated to boiling under reflux for a further 2 hours and then evaporated in vacuo at 10 mbar and the residue is dried to constant weight.
  • the polymer only partially dissolves in water, but well in tetrahydrofuran, isopropanol and ethyl acetate.
  • Acrylamide derivative 3 40 g of N- (isobutoxymethyl) acrylamide and 10 g of acrylic acid in 100 g of tetrahydrofuran, polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran and then neutralized with 11 g of 50% sodium hydroxide solution and by adding 200 g Diluted water. After the tetrahydrofuran has been distilled off, a slightly cloudy solution with a solids content of 38% and a viscosity of 3420 mPas is obtained. The K value is 19.1 (determined on solutions of the polymer in THF).
  • Polymer 19 As described for the preparation of polymer 14, 50 g
  • Acrylamide derivative 3 40 g of N- (isobutoxymethyl) acrylamide and 10 g of acrylic acid in 100 g of tetrahydrofuran, polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran and by adding 11 g of 50% strength
  • the solution obtained contains 26.3% neutralized copolymer, the K value of which is 60.2 (measured 1% in water).
  • 60 g of tetrahydrofuran are placed in a mechanically stirred 250 ml round-bottomed flask with a reflux condenser and metering devices and heated to boiling.
  • a solution of 20 g of acrylamide derivative 1 and 60 g of acrylic acid in 50 g of tetrahydrofuran and 20 g of N-vinylpyrrolidone, dissolved in 20 g of tetrahydrofuran, are metered into this template within 30 minutes.
  • an initiator solution consisting of 2 g of 75% tert-butyl perpivalate and 30 g of tetrahydrofuran is added dropwise within 40 minutes.
  • the mixture is refluxed for a further hour, allowed to cool and neutralized with 140 g of 25% strength aqueous sodium hydroxide solution.
  • the tetrahydrofuran is distilled off and the solution of the copolymer obtained is adjusted to 30% by weight solids content by adding water.
  • the K value is 48.3 (measured in a 1% strength aqueous solution).
  • tetrahydrofuran 125 g of tetrahydrofuran are placed in a 500 ml 4-necked flask with stirrer, reflux condenser and 4 metering devices and heated to boiling. 53 g of acrylic acid and simultaneously 23 g of acrylamide derivative 4 dissolved in 35 g of tetrahydrofuran are metered in over the course of 2 hours, and a solution of 1.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 20 g of tetrahydrofuran is added within 2.5 hours . The mixture is refluxed for a further hour and cooled. 109 g of triethanolamine are added to the solution of the copolymer within 30 minutes and the mixture is diluted with 100 g of water. After the tetrahydrofuran has been distilled off, a solids content of 40% is established. The K value (measured in a 1% aqueous solution) is 27.8. Application testing of the polymers as
  • the polymers to be used according to the invention significantly improve the primary washing action of the detergent formulations. At the same time, an improvement in the graying inhibition is observed.
  • the polymers to be used according to the invention can be incorporated into the detergent formulations A and B without problems and result in stable, homogeneous solutions.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On utilise comme additifs d'agents de lavage et de nettoyage à teneur réduite ou nulle en phosphates des polymères qui contiennent en tant que monomère essentiel au moins 5 % en poids d'amides polymérisés d'acides N-(alcoxy-polyalcoxyméthyl)carboxyliques monoéthyléniquement insaturés contenant 3 à 8 atomes de C, en quantités suffisantes pour accroître la capacité primaire et secondaire de lavage de ces agents. L'invention concerne également des agents contenant les polymères décrits.
PCT/EP1991/001360 1990-07-27 1991-07-19 Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage Ceased WO1992002606A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59103296T DE59103296D1 (de) 1990-07-27 1991-07-19 Verwendung von n-(alkyloxy-polyalkoxymethyl) carbonamid-gruppen aufweisenden polymerisaten als zusatz zu wasch- und reinigungsmitteln.
EP91912925A EP0541588B1 (fr) 1990-07-27 1991-07-19 Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4023820A DE4023820A1 (de) 1990-07-27 1990-07-27 Verwendung von n-(alkyloxy-polyalkoxymethyl)carbonamid-gruppen aufweisenden polymerisaten als zusatz zu wasch- und reinigungsmitteln
DEP4023820.2 1990-07-27

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WO1992002606A1 true WO1992002606A1 (fr) 1992-02-20

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PCT/EP1991/001360 Ceased WO1992002606A1 (fr) 1990-07-27 1991-07-19 Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage

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EP (1) EP0541588B1 (fr)
JP (1) JPH05509118A (fr)
AT (1) ATE113069T1 (fr)
CA (1) CA2081199A1 (fr)
DE (2) DE4023820A1 (fr)
WO (1) WO1992002606A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1098903C (zh) * 1996-06-05 2003-01-15 阿斯特拉公司 生物相容性胶

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0116930B1 (fr) * 1983-02-18 1986-08-06 BASF Aktiengesellschaft Copolymères, leur préparation et leur usage dans les produits de lavage et de nettoyage
EP0063018B1 (fr) * 1981-04-10 1986-12-03 Rohm And Haas Company Copolymères d'acrylamide utilisables comme agent épaississant pour compositions aqueuses et compositions aqueuses le contenant
DE3716543A1 (de) * 1987-05-16 1988-11-24 Basf Ag Verwendung von wasserloeslichen copolymerisaten, die monomere mit mindestens zwei ethylenisch ungesaettigten doppelbindungen einpolymerisiert enthalten, in wasch- und reinigungsmitteln
EP0368214A2 (fr) * 1988-11-10 1990-05-16 BASF Aktiengesellschaft Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides
US4946627A (en) * 1989-07-19 1990-08-07 National Starch And Chemical Investment Holding Corporation Hydrophobically modified polycarboxylate polymers utilized as detergent builders

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0063018B1 (fr) * 1981-04-10 1986-12-03 Rohm And Haas Company Copolymères d'acrylamide utilisables comme agent épaississant pour compositions aqueuses et compositions aqueuses le contenant
EP0116930B1 (fr) * 1983-02-18 1986-08-06 BASF Aktiengesellschaft Copolymères, leur préparation et leur usage dans les produits de lavage et de nettoyage
DE3716543A1 (de) * 1987-05-16 1988-11-24 Basf Ag Verwendung von wasserloeslichen copolymerisaten, die monomere mit mindestens zwei ethylenisch ungesaettigten doppelbindungen einpolymerisiert enthalten, in wasch- und reinigungsmitteln
EP0368214A2 (fr) * 1988-11-10 1990-05-16 BASF Aktiengesellschaft Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides
US4946627A (en) * 1989-07-19 1990-08-07 National Starch And Chemical Investment Holding Corporation Hydrophobically modified polycarboxylate polymers utilized as detergent builders

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1098903C (zh) * 1996-06-05 2003-01-15 阿斯特拉公司 生物相容性胶

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CA2081199A1 (fr) 1992-01-28
EP0541588A1 (fr) 1993-05-19
JPH05509118A (ja) 1993-12-16
ATE113069T1 (de) 1994-11-15
DE4023820A1 (de) 1992-01-30
EP0541588B1 (fr) 1994-10-19
DE59103296D1 (de) 1994-11-24

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