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EP0828763A1 - Melanges de polymeres et de tensio-actifs, leur procede de preparation et leur utilisation - Google Patents

Melanges de polymeres et de tensio-actifs, leur procede de preparation et leur utilisation

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Publication number
EP0828763A1
EP0828763A1 EP96917392A EP96917392A EP0828763A1 EP 0828763 A1 EP0828763 A1 EP 0828763A1 EP 96917392 A EP96917392 A EP 96917392A EP 96917392 A EP96917392 A EP 96917392A EP 0828763 A1 EP0828763 A1 EP 0828763A1
Authority
EP
European Patent Office
Prior art keywords
monomers
mixtures
weight
formula
ethylenically unsaturated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96917392A
Other languages
German (de)
English (en)
Inventor
Christian Schade
Dieter Boeckh
Axel Sanner
Hans-Ulrich JÄGER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0828763A1 publication Critical patent/EP0828763A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C08F26/00—Homopolymers and 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/02—Homopolymers and 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • 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
    • C08F26/00—Homopolymers and 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/06—Homopolymers and 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/24—Treatment of polymer suspensions
    • 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
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the invention relates to mixtures of polymers of vinylimidazoles, vinylpyrrolidone, open-chain vinylamides, N-vinyloxazolidone or N-vinyltriazole and optionally other copolymerizable monoethylenically unsaturated monomers and, where appropriate, monomers with at least 2 ethylenically unsaturated, non-conjugated double bonds and surfactants, Process for the preparation of the mixtures and the use of the mixtures as an additive to detergents.
  • Polymers of 1-vinylimidazole are prepared, for example, by radical polymerization of 1-vinylimidazole in aqueous solution or in alcohols, cf. DE-A-28 14 287.
  • To produce high molecular weight or crosslinked polymers of 1-vinylimidazole one can use the precipitation polymerization in benzene, cf. EP-A-0 162 388.
  • the precipitation polymerization of 1-vinylimidazole in carbon tetrachloride, benzene or toluene is known from European Polymer Journal, volume 24, 1019 (1988).
  • the polyvinylimidazoles produced in carbon tetrachloride have only low molar masses, while the polymers produced in benzene or toluene are obtained as crosslinked gels.
  • WO-A-92/07011 discloses the production of weakly crosslinked, highly swellable polyvinylpyrrolidones by polymerizing N-vinylpyrrolidone in, for example, aliphatic hydrocarbons.
  • the polymers obtainable in this way are isolated by filtration, washing and drying or by direct drying of the reaction mixture.
  • the known processes have the disadvantage that the organic solvents used are toxicologically unsafe or easily flammable.
  • the polymers obtained must be isolated from these solvents and some of them have to be laboriously cleaned.
  • the present invention has for its object to provide polymers in a formulation that can be used directly and without isolation of the polymers.
  • the object is achieved according to the invention with mixtures of polymers and surfactants if they comprise 1 to 50% by weight of a polymer
  • R 1 , R 2 and R 3 are the same or different and represent H, Ci to C 4 alkyl, monomers of the formula
  • H 2 C CH NCR 5 ( II ) ,
  • R 4 and R 5 are the same or different and represent H, Ci to C 4 alkyl or form a ring from 3 to 5 methylene groups with one another,
  • N-vinyloxazolidone N-vinyltriazole, 4-vinylpyridine-N-oxide or mixtures of the monomers mentioned,
  • the invention also relates to a process for the preparation of the mixtures, in which
  • R 1 , R 2 and R 3 are the same or different and represent H, Ci to C 4 alkyl, monomers of the formula
  • R 4 and R 5 are the same or different and represent H, C 1 -C 4 -alkyl or form a ring from 3 to 5 methylene groups with one another,
  • N-vinyloxazolidone N-vinyltriazole, 4-vinylpyridine-N-oxide or mixtures of the monomers mentioned,
  • Monomers of the formula I are, for example, 1-vinylimidazole, 2-methyl-l-vinylimidazole, 2-ethyl-l-vinylimidazole, 2-propyl-l-vinylimidazole, 2-butyl-l-vinylimidazole, 2,4-dimethyl-l- vinylimidazole, 2,5-dimethyl-l-vinylimidazole, 2-ethyl1-4-methyl-l-vinylimidazole, 2-ethyl-5-methyl-l-vinylimidazole, 2,4,5-trimethyl-l-vinylimidazole, 4,5-diethyl-2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 5-methyl-1-vinylimidazole, 4-ethyl-1-vinylimidazole, 4, 5-dimethyl-1-vinylimidazole or 2, 4,5-triethyl-1-vinylimi
  • Monomers of the formula II are open-chain and cyclic N-vinylamides, for example N-vinylformamide, N-vinylacetamide, N-methyl-N-vmylacetamide, N-vinylpyrrolidone, N-vinylpiperidone or N-vinylcaprolactam.
  • N-vinylpyrrolidone is preferably used to prepare the mixtures according to the invention.
  • Particularly preferred monomers of group a) are 1-vinylimidazole, 1-vinyl-2-methylimidazole or 1-vinylpyrrolidone and mixtures of the monomers mentioned in any ratio.
  • the polymers contain at least 10% by weight of the monomers a) in polymerized form.
  • the monomers a) are used in amounts of 10 to 100, preferably 50 to 100, in particular 85 to 99.5% by weight, based on the total amount of the monomers used in the polymerization.
  • Suitable monomers of group b) are other monoethylenically unsaturated monomers copolymerizable with the monomers of group a). Examples of such monomers are
  • (Meth) acrylic esters such as methyl, ethyl, hydroxyethyl, propyl, hydroxypropyl, butyl, ethylhexyl, decyl, lauryl, i-bornyl, cetyl, palmityl, phenoxyethyl or stearyl acrylate or the corresponding methacrylates ,
  • crylamides such as acrylamide, N-methylol-acrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N-tert-butylacrylamide, N-tert-octyl-acrylamide, N-undecylacrylamide or the corresponding Methacrylic amides, vinyl esters with 2 to 30, in particular 2 to 14 carbon atoms in the molecule, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl neooctane acid, vinyl neonate acid, vinyl
  • Suitable monomers of group c) are compounds with at least 2 ethylenically unsaturated, non-conjugated double bonds in the molecule. Connections of this type are crosslinkers. Suitable crosslinkers are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols can be wholly or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
  • Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol , But-2-en-l, 4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1, 6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1 , 12-dodecanediol, neopentyl glycol, 3-methylpentane-l, 5-diol, 2, 5-dimethyl-l, 3-hexanediol, 2,2,4-trimethyl-l, 3-pentanediol, 1,2-cyclohexane
  • 1,4-cyclohexanediol 1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyDpropane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane , Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol, as well as polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of 200 to 10,000 in each case.
  • Block copolymers of ethylene oxide or propylene oxide or copolymers which contain ethylene oxide and propylene oxide groups built in
  • underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythri, 1,2,5-pentane triol, 1,2, 6-hexanetriol, trie hoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose, of course the polyhydric alcohols can also be reacted with ethylene oxy d or propylene oxide can be used as the corresponding ethoxylates or propoxylates.
  • the polyhydric alcohols can also first be converted into the corresponding glycidyl ethers by reaction with epichlorohydrin.
  • crosslinkers are the Vinylester or the esters of monohydric unsaturated alcohols with ethylenically unsaturated C 3 - to C ß -Carbonsauren, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • examples of such alcohols are allyl alcohol, l-buten-3-ol, 5-hexen-l-ol, l-octen-3-ol, 9-decen-l-ol, dicyclopentenyl alcohol, 10-undecen-l-ol , Cinnamon alcohol, citronellol, crotyl alcohol or cis-9-octadecen-l-ol.
  • you can also esterify the monohydric, unsaturated alcohols with polyhydric carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • crosslinking agents are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to aliphatic hydrocarbons, e.g. Divinylbenzene, divinyltoluene, 1.7-0ctadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes with molecular weights of 200-20,000.
  • crosslinking agents are acrylic acid amides, methacrylic acid amides and N-allyl amines of at least divalent amines.
  • Such amines are, for example, diaminomethane, 1,2-diaminoethane, 1,3-diammopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine.
  • the amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above, are also suitable.
  • crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane. Mixtures of the aforementioned compounds can of course also be used. Those crosslinkers which are soluble in the reaction mixture are preferably used.
  • crosslinkers are methylenebisacrylamide, di- and triallylamine, divinylimidazole, divinylethylene urea, reaction products of polyhydric alcohols with acrylic or methacrylic acid, methacrylic acid esters and acrylic acid esters of polyalkylene oxides or of polyhydric alcohols, which are mixed with ethylene oxide and / or propylene oxide and / / or epichlorohydrin have been reacted, allyl methacrylate and divinylbenzene.
  • Methylene bisacrylamide, N, N'-divinylethylene urea, acrylic acid and methacrylic acid esters of at least dihydric C 2 to C 4 alcohols, allyl methacrylate and divinylbenzene are very particularly preferred.
  • crosslinkers are used in the polymerization, they can be present in amounts of up to 30, preferably from 0.2 to 20 and very particularly preferably from 0.5 to 10% by weight to the total monomers used in the polymerization.
  • the mixtures according to the invention consist of polymers and surfactants.
  • Suitable surfactants are described, for example, in M. and I. Ash, Handbook of Industrial Surfactants, Gower Publishing Co., Hants, 1993.
  • Surfactants can be low molecular weight or polymeric compounds.
  • Nonionic surfactants are particularly preferred.
  • Low molecular weight, nonionic surfactants generally contain a straight-chain or branched, saturated or unsaturated, cyclic or acyclic, aromatic or aliphatic alkyl radical with 8 to 40, preferably 10 to 30, very particularly preferably 12 to 22 carbon atoms in the molecule.
  • the alkyl radical can also be completely or partially fluorinated.
  • the alkyl radical is bound to a hydrophilic part of the molecule which contains at least one oxygen or nitrogen atom.
  • Preferred compounds are, for example, ethers and esters of sugars or sugar derivatives, such as sucrose esters, mannose esters, xylose esters or sorbitan esters, esters and ethers of glycerol, diglycerol, polyglycerol or glycerol sugar condensates, ceramides and glycosyl ceramides, fatty acid alkanolair.de such as fatty acid ethanolamides, fatty acid isopropanolamides, fatty acid diethanolamides, fatty acid poly-diethanolamides, N-alkylpyrrolidone derivatives, pyrrolidone-5-carboxylic acid alkyl esters, citric and tartaric acid esters, Ci- to Ci ⁇ -alkyl (poly) glycosides, hydroxyalkylpolyesteric acid compounds of polyhydroxy compounds such as polypropane compounds , Erythritol, pentaerythri, neopentyl
  • Further surface-active compounds a) are sorbitan esters, sucrose esters or glycerol esters of Cs to C 3 o ⁇ carboxylic acids or alkoxylation products of these esters.
  • the above-mentioned esters are preferably derived from C 2 to C 22 carboxylic acids.
  • Alkoxylation products should preferably be understood to mean the addition products of ethylene oxide with the esters. Up to 80 moles of ethylene oxide can be added per mole of the esters in question. Addition products are also suitable of ethylene oxide and propylene oxide and / or of butylene oxides to the esters as surface-active compounds. Alkyldimethylamine oxides are also suitable.
  • Polymeric surfactants which contain ethylene oxide and / or propylene oxide units as the hydrophilic part of the molecule are uncrosslinked and have molecular weights from 500 to 100,000, preferably 700 to 20,000.
  • the polymeric surfactants can contain at least one hydrophobic block Contain block or they are composed of a hydrophilic chain with comb-like arranged hydrophobic branches.
  • the hydrophilic part of the polymeric surfactants is formed by homopolymers made from ethylene oxide or propylene oxide or by block copolymers made from ethylene oxide and propylene oxide, and by block and comb polymers with blocks made of polyethylene oxide, polypropylene oxide or polyco (ethylene oxide, propylene oxide), while
  • the hydrophobic part of the polymeric surfactants in blocks consists of polystyrenes, polyalkyl (meth) acrylates, silicone oils, polyhydroxy fatty acids, polyamidoamines, polyisobutylene or polytetrahydrofurans.
  • General polymers which have at least one amino group, a hydroxyl group which can be detonated with bases or an anionic group and have a molar mass of 100 to 5000, such as ethylene oxide, propylene oxide or mixtures thereof, can also be converted into suitable polymeric surfactants .
  • addition products of ethylene oxide and / or propylene oxide with Cio to C3o alcohols, alkylphenols, fatty amines or fatty acids, sucrose esters, sorbitan esters, (poly) glycerol esters or their corresponding ethoxylates and alkyl (poly) glycosides are particularly preferred .
  • Addition products of ethylene oxide and / or propylene oxide with C 2 -C 22 -alcohols or alkylphenols, sorbitan esters, glycerol esters or their corresponding ethoxylates with 12 to 22 carbon atoms in the alkyl chain and alkyl (poly) glycosides with 8 are very particularly preferred up to 22 carbon atoms in the alkyl chain.
  • the surfactants have, for example, a softening point below 100 ° C., preferably below 60 ° C. and particularly preferably below 40 ° C.
  • the polymers from the monomers a) and optionally b) and / or optionally c) are known. They can be produced by various processes. Reverse suspension or emulsion polymerization are particularly suitable processes, an aqueous solution of the monomers being emulsified and polymerized in an inert organic liquid, and precipitation polymerization. Protective colloids or emulsifiers can expediently be used in the water-in-oil polymerization. After the end of the polymerization, the water can, for example removed by azeotropic distillation and the inert organic solvent is replaced by a nonionic surfactant, for example by distilling off the inert organic solvent and preferably adding an amount of surfactants corresponding to the amount distilled off.
  • solvents suitable for water-in-oil emulsion polymerization are, for example, saturated, straight-chain, branched or cyclic hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane or isooctane, aliphatic ethers such as dimethyl ether, diethyl ether, diamyl ether, tert-butyl
  • ketones such as acetone, methyl ethyl ketone, diethyl ketone or methyl amyl ketone
  • cis to cis carboxylic acid esters for example ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, stearyl acetate, ethylhexyl ethyl acetate, Propyl myristate or iso-pro
  • silicone oils such as octamethyl-cyclotetrasilane, liquid or supercritical carbon dioxide, aromatic hydrocarbons such as toluene or xylene.
  • these inert organic solvents are largely exchanged for a surfactant.
  • the mixtures are preferably obtainable by free-radically initiated polymerization of a) 10 to 100% by weight of at least one vinylimidazole of the formula
  • R 1 , R 2 and R 3 are identical or different and stand for H, Ci to C 4 alkyl,
  • R 4 and R 5 are the same or different and represent H, Ci to C 4 alkyl or form a ring from 3 to 5 methylene groups with one another,
  • N-vinyloxazolidone N-vinyltriazole, 4-vinylpyridine-N-oxide or mixtures of the monomers mentioned,
  • the mixtures according to the invention can of course also be prepared by polymerizing the monomers in a mixture of a solvent and a surfactant in any ratio, the solvents being removed as completely as possible from the reaction mixture following the polymerization.
  • the amount of the organic phase is preferably selected in the polymerization so that the resulting reaction mixture can be stirred during the polymerization.
  • the solids content of the mixtures is, for example, in the range from 1 to 60, preferably 15 to 40,% by weight.
  • Small amounts for example up to 10% by weight, preferably up to 4% by weight, based on the monomers used, of water, methanol, ethanol, isopropanol or protective colloids can also be added to the reaction mixture in order to increase the solubility of individual components To improve the reaction mixture or to influence the properties of the resulting copolymers.
  • the morphology of the polymers can be influenced in the presence of protective colloids in such a way that mixtures are obtained which have a particularly high polymer content.
  • Suitable protective colloids are, for example, polyvinyl pyrrolidones with K values from 10 to 100, partially saponified polyvinyl acetates, cellulose ethers, copolymers of maleic acid or maleic anhydride with alkenes, preferably isobutylene or diisobutylene or copolymers of N-pyrrolidone and vinyl acetate. If water is also used in the precipitation polymerization, it is used only in such amounts that the mixture of all components still appears homogeneous before the start of the polymerization.
  • the molecular weight of the resulting polymers can, if appropriate, be reduced by adding regulators to the polymerizing mixture.
  • regulators for example, halogen compounds such as Use carbon tetrachloride, chloroform, bromotrichloromethane, allyl compounds such as allyl alcohol or 2, 5-diphenyl-l-hexene, aldehydes, formic acid or formic acid esters.
  • compounds which contain sulfur in bound form are preferably used as polymerization regulators, for example hydrogen sulfites, sulfites, disulfites and dithionites or compounds which contain sulfur bound to a carbon atom, such as organic sulfides, disulfides, polysulfides, sulfoxides, sulfones and mercapto compounds .
  • Mercapto alcohols, mercaptocarboxylic acids and mercaptoalkanes with 2 to 30 carbon atoms in the molecule are particularly preferably used, for example 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, cysteine, mercaptoacetic acid, 3- Mercaptopropionic acid, mercaptosuccinic acid, n-butyl mercaptan, n-hexyl mercaptan, n-dodecyl mercaptan or tert-dodecyl mercaptan.
  • polymerization regulators are used, they are used in amounts of 0.1 to 10, preferably 0.1 to 5% by weight, based on the monomers in the reaction mixture.
  • the monomers specified above are usually polymerized using free-radical initiators, generally in an inert gas atmosphere.
  • Hydrogen peroxide or inorganic persulfates can be used as radical initiators, as can organic compounds of the peroxide, peroxyester, percarbonate or azo type, such as e.g.
  • initiators 2,2'-azobis (2-methylbutyronitrile) and dimethyl-2,2'-azobis (isobutyrate). You can of course also use initiator mixtures or the known redox initiators. It is preferable to use initiators which - if the polymerization is carried out in surfactants - are more than 5% by weight soluble in the surfactants at 25 ° C. The initiators are used in the usual amounts, e.g. in amounts of 0.02 to 5% by weight, based on the monomers to be polymerized.
  • the precipitation polymerization is usually carried out under an inert gas atmosphere.
  • the polymerization can be carried out, for example, by placing all the components which are present during the polymerization in a polymerization vessel, starting the reaction and, if appropriate, cooling the reaction mixture in order to control the polymerization temperature.
  • the monomers are generally polymerized at temperatures of 40 to 200, preferably 50 to 120 ° C.
  • the temperature can be controlled differently during the reaction according to a program.
  • the polymerization is preferably carried out under atmospheric pressure, but can also be carried out under reduced or elevated pressure. If the polymerization temperature is above the boiling point of the solvent used, the polymerization is carried out in pressure-tight apparatus at pressures up to 16 bar.
  • Polymers which contain 4-vinylpyridine-N-oxide (formally) as copolymerized units are preferably prepared by polymerization or copolymerization of 4-vinylpyridine and subsequent N-oxidation of the pyridine ring with e.g. Peracetic acid produced in situ.
  • the polymers which have basic, N-containing groups, can be converted into a quaternized form after the reaction by means of a suitable reagent.
  • a suitable reagent for quaternization, for example, alkyl halides with 1 to 18 carbon atoms in the molecule, for example methyl chloride, ethyl chloride, propyl chloride, hexyl chloride, dodecyl chloride or lauryl chloride, and benzyl halides such as benzyl chloride are suitable.
  • the corresponding iodine or bromine compounds are of course also suitable.
  • Suitable quaternizing agents are also dialkyl sulfates, especially dimethyl sulfate and diethyl sulfate. In some cases, it is also sufficient to convert the polymers into the salt form by treatment with an acid. The quaternization can take place completely or partially. 12
  • the reaction mixture can be subjected to a physical or chemical aftertreatment.
  • Such processes are, for example, the known processes for reducing residual monomers, e.g. an aftertreatment by adding polymerization initiators or mixtures of several polymerization initiators at suitable temperatures or heating the polymerization solution to temperatures above the polymerization temperature, an aftertreatment of the polymer solution by means of steam or stripping with nitrogen or treating the reaction mixture with oxidizing or reducing reagents.
  • the polymers are soluble in water, they have K values of 10 to 300 (determined according to H. Fikentscher in aqueous solution at 25 ° C. and a polymer concentration of 1).
  • the average diameter of the polymers is, for example, 0.1 to 1000, preferably 0.5 to 80 ⁇ .
  • the suspensions of the copolymers in the surfactants according to the invention are used, for example, as an additive for pharmaceutical or cosmetic preparations, as an additive in papermaking, for stabilizing enzymes or for adsorbing metal ions, dyes or acids.
  • Use as an additive to detergents is particularly preferred.
  • the polymers inhibit the transfer of dye to the non-colored textiles.
  • the crosslinked copolymers of N-vinylimidazole and N-vinylpyrrolidone are particularly suitable for use in heavy-duty detergents because they are particularly suitable for small detergents Dye concentrations in the wash liquor are significantly more effective than soluble polymers.
  • the detergents can be in powder form or can also be in liquid form.
  • the composition of the detergents and cleaners can be very different. Washing and cleaning supply ⁇ formulations normally contain from 2 to 50 weight surfactants and builders, if necessary. This information applies to both liquid and powder detergents. Detergent and cleaner formulations that are used in Europe, the United States and are common in Japan can be found, for example, in Chemical and Engn. News, volume 67, 35 (1989). Further information on the composition of detergents and cleaning agents can be found in Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63 to 160.
  • the detergents can optionally also contain a bleach, for example sodium perborate or sodium percarbonate, which, if used, can be present in the detergent formulation in amounts of up to 30% by weight.
  • the detergents or cleaning agents can optionally be other conventional ones
  • Contain additives e.g. Complexing agents, opacifiers, optical brighteners, enzymes, perfume oils, other color transfer inhibitors, graying inhibitors, soil release polymers and / or bleach activators. They contain the mixtures according to the invention in amounts of 0.1 to 10, preferably 0.2 to 3% by weight.
  • Table 1 contains the washing conditions for the examples.
  • the composition of the detergents used is given in Table 2.
  • the staining of the test fabric was measured photometrically.
  • the respective color strengths of the stains were determined from the reflectance values measured on the individual test fabrics according to the method described in A. Kud, Seifen, ⁇ le, Fette, Wachsen, Volume 119, 590-594 (1993). From the color strengths for the test with the respective test substance, the color strength for the test without test substance and the color strength of the test fabric before washing, the The process described in literature describes the color transfer inhibiting activity of the test substance in% (color transfer inhibition is treated analogously to graying inhibition). The efficacies are listed in Table 3 for the different dyes.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne des mélanges de polymères et de tensio-actifs contenant, en suspension dans au moins un tensio-actif, entre 1 et 50 % en poids d'un polymère constitué de: a) entre 10 et 100 % en poids d'au moins 1 vinylimidazole ou d'un dérivé de celui-ci, d'un N-vinylamide, N-vinyloxazolidone, N-vinyltriazole cycliques ou à chaîne ouverte, ou de mélanges desdits monomères; b) entre 0 et 90 % en poids d'autres monomères copolymérisables mono-éthyléniquement insaturés; et c) entre 0 et 30 % en poids d'au moins un monomère présentant au moins deux doubles liaisons éthyléniquement insaturées. L'invention concerne également un procédé permettant de produire ces mélanges par polymérisation desdits monomères dans un tensio-actif, ainsi que leur utilisation en tant qu'additifs pour produits de lavage.
EP96917392A 1995-05-26 1996-05-21 Melanges de polymeres et de tensio-actifs, leur procede de preparation et leur utilisation Withdrawn EP0828763A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1995119338 DE19519338A1 (de) 1995-05-26 1995-05-26 Mischungen aus Polymeren und Tensiden, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19519338 1995-05-26
PCT/EP1996/002178 WO1996037524A1 (fr) 1995-05-26 1996-05-21 Melanges de polymeres et de tensio-actifs, leur procede de preparation et leur utilisation

Publications (1)

Publication Number Publication Date
EP0828763A1 true EP0828763A1 (fr) 1998-03-18

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EP96917392A Withdrawn EP0828763A1 (fr) 1995-05-26 1996-05-21 Melanges de polymeres et de tensio-actifs, leur procede de preparation et leur utilisation

Country Status (5)

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EP (1) EP0828763A1 (fr)
JP (1) JPH11505869A (fr)
CA (1) CA2219071A1 (fr)
DE (1) DE19519338A1 (fr)
WO (1) WO1996037524A1 (fr)

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
FR2777893B1 (fr) * 1998-04-28 2004-08-06 Rhodia Chimie Sa Polymeres a base de monomeres heterocycliques insatures, et leur mise en oeuvre dans les procedes de reticulation
ES2678773B1 (es) * 2017-01-16 2019-06-12 Consejo Superior Investigacion Recubrimientos tipo hidrogel en base vinil-lactamas

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
DE2814287A1 (de) * 1978-04-03 1979-10-11 Henkel Kgaa Waschmittel mit einem gehalt an verfaerbungsinhibierenden zusaetzen
DE4421179A1 (de) * 1994-06-17 1995-12-21 Basf Ag Farbstoffübertragungsinhibitoren für Wasch- und Reinigungsmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9637524A1 *

Also Published As

Publication number Publication date
JPH11505869A (ja) 1999-05-25
WO1996037524A1 (fr) 1996-11-28
CA2219071A1 (fr) 1996-11-28
DE19519338A1 (de) 1996-11-28

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