EP0828763A1

EP0828763A1 - Polymer and surfactant mixtures, process for their preparation and their use

Info

Publication number: EP0828763A1
Application number: EP96917392A
Authority: EP
Inventors: Christian Schade; Dieter Boeckh; Axel Sanner; Hans-Ulrich JÄGER
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1995-05-26
Filing date: 1996-05-21
Publication date: 1998-03-18
Also published as: JPH11505869A; WO1996037524A1; CA2219071A1; DE19519338A1

Abstract

The invention concerns polymer and surfactant mixtures containing in suspended form in at least one surfactant between 1 and 50 wt.% of a polymer comprising: a) between 10 and 100 wt.% of at least one vinylimidazole or a derivative thereof, an open-chain or cyclic N-vinylamide, N-vinyloxazolidone, N-vinyltriazole or mixtures of said monomers; b) between 0 and 90 wt.% of other copolymerizable monoethylenically unsaturated monomers; and c) between 0 and 30 wt.% of at least one monomer with at least two ethylenically unsaturated, non-conjugated double bonds. The invention further concerns a process for preparing these mixtures by polymerization of said monomers in a surfactant, and the use of the mixtures as additives for washing agents.

Description

Mixtures of polymers and surfactants, process for their preparation and their use

description

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. In addition, the precipitation polymerization of 1-vinylimidazole in carbon tetrachloride, benzene or toluene is known from European Polymer Journal, volume 24, 1019 (1988). However, 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. In addition, it is an object of the invention to develop a process for the preparation of polymers containing imidazole and / or lactam groups, which dispenses with the use of toxicologically questionable solvents. 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

a) 10 to 100 wt .-% of at least one vinylimidazole of the formula

R ⁱ

H ₂ C == CH — KΓ ^ N (I!

Y ^ ^ R3

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

O ||

H ₂ C = CH NCR ^{5 (} II ⁾ ,

R4

in which 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,

b) 0 to 90% by weight of other copolymerizable monoethylenically unsaturated monomers and

c) 0 to 30% by weight of at least one monomer with at least two ethylenically unsaturated, non-conjugated double bonds

contained in suspended form in at least one surfactant.

The invention also relates to a process for the preparation of the mixtures, in which

a) 10 to 100 wt .-% of at least one vinylimidazole of the formula R ^l

H ₂ C = CH N '"^ N (I)» ^^ R ³

H ₂ C = CH NCR ⁵ : II:

R ⁴

in which 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,

free-radically polymerized in at least one surfactant at temperatures of at least 50 ° C. or in which the monomers (a) and optionally (b) and / or optionally (c) are polymerized radically in the aqueous phase of a water-in-oil suspension and after At the end of the polymerization, the oil phase of the water-in-oil suspension is replaced by at least one surfactant.

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-vinylimidazole. Mixtures of the monomers mentioned can be used in any ratio. 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. Of the compounds of the formula II, 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.

Other 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 , (Meth) 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 neodecanoate, styrene, vinyl toluene, α-methylstyrene, unsaturated carboxylic acid, methacrylic acid, such as acrylic acid, such as acrylic acid , Maleic acid, fumaric acid, itaconic acid or its corresponding anhydrides, 2-acrylamido-2-methylpropanesulfonic acid, acrylic esters, which have a basic N atom, such as diethylaminoethyl acrylate, dimethylaminoethyl acrylate, dimeth yla inopropyl acrylate or the corresponding methacrylic esters, 2-vinyl pyridine or 4-vinyl pyridine. Alkyl (meth) acrylic esters, vinyl acetate, styrene, acrylic acid, methacrylic acid, maleic acid and monomers which have a basic N atom are particularly preferred.

If the monomers b) are used, they are present in amounts of up to 90, preferably up to 50,% by weight, based on the total amount of all monomers. 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-cyclohexanediol ,

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. In addition to the homopolymers or propylene oxides of ethylene oxide Block copolymers of ethylene oxide or propylene oxide or copolymers which contain ethylene oxide and propylene oxide groups built in. Examples of 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.

Further suitable 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. But 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.

Other suitable 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.

Also suitable are 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. Also suitable as 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. Also suitable are N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example urea, ethylene urea, propylene urea or tartaric acid diamide.

Other 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. Particularly preferred 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. If 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 Ciβ-alkyl (poly) glycosides, hydroxyalkylpolyesteric acid compounds of polyhydroxy compounds such as polypropane compounds , Erythritol, pentaerythri, neopentyl diglycol, triethanolamine or condensates derived therefrom, alkoxylates, in particular the addition products of ethylene oxide and / or propylene oxide to the compounds listed above and to oxo alcohols, C ₃ -C ₃ -alcohols, alkylphenols, fatty acid amides, Fatty amines, fatty acids and derivatives such as hydroxycarbon acidic where the polyalkylene oxide chains can be modified on one or both sides. In the case of modification on both sides, the modifying proportions can be the same or different and, for example, can also partly represent a Ci to C ₄ ether function.

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. In addition to at least one hydrophilic block, 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 .

Of the above-mentioned 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.

In the case of precipitation polymerization, those solvents are used which at least partially dissolve the monomers, but not the resulting polymers, so that they precipitate in finely divided form. 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

15 methyl ether or dibutyl ether, 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

20 pylpalmitate, silicone oils such as octamethyl-cyclotetrasilane, liquid or supercritical carbon dioxide, aromatic hydrocarbons such as toluene or xylene. After the polymerization, these inert organic solvents are largely exchanged for a surfactant.

25

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

-30

Rl

H ₂ C = CH- • N ' ^• N (I)

35 R ² ' ^* R ³

in which R ¹ , R ² and R ^{3 are} identical or different and stand for H, Ci to C ₄ alkyl,

Monomers of the formula

40

45 in which 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,

in at least one surfactant.

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. For example, 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. 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. However, 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. If 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. Dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl perpivalate, t-amyl perpivalate, t-butyl perneodecanoate, 2,2'-azobis (2-amidino-propane) dihydrochloride, 4,4'-azobis ( 4-cyanovaleric acid), 2,2'-azobis [2- (2-imιdazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile,

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. However, one can also proceed in such a way that only a few or some of the components are initially charged, the polymerization starts and the rest of the components are added individually or together at different intervals, depending on the progress of the polymerization, continuously or batchwise. However, one can also proceed in such a way that initially only the diluent is initially introduced and the monomers and the polymerization initiator are introduced into the initial batch or continuously in separate feeds.

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.

In the production of crosslinked copolymers, it is known that the coatings on the walls of the reaction vessels and on the Ruhr are often difficult to remove. When the mixtures according to the invention are prepared by copolymerizing the monomers in preferably nonionic surfactants as precipitants, the otherwise disruptive deposit formation is practically not observed.

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. 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

After the polymerization process, 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.

If 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 μ.

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. When washing colored and white textiles, the polymers inhibit the transfer of dye to the non-colored textiles. In particular, 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. However, in the case of full laundry, mainly white and lightly colored laundry as well as laundry that is very washfast are washed. Laundry that gives off a large amount of dye is usually only inadvertently and therefore contained in the laundry in a very small proportion, e.g. if a colored

Sock is washed. The crosslinked copolymers, which bind small amounts of dye significantly more strongly than water-soluble color transfer inhibitors, therefore have a great advantage in use over the water-soluble products.

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.

Examples

example 1

In a 2000 ml flask equipped with a stirrer, reflux condenser, thermometer and an apparatus for working under protective gas, 440 g of a C ₁₃ / C ₁₅ -OXO alcohol were reacted with 7 units of ethylene oxide per molecule 50 g of N-vinylimidazole, 50 g of N-vinylpyrrolidone, 5 g of divinylethylene urea and 1 g of tert-butyl perpivalate had been heated to 80 ° C. with stirring. The mixture was stirred at this temperature for 5 hours. A finely divided, white polymer suspension with an average particle size of 14.3 μm was obtained. The suspension could easily be poured out of the polymerization vessel without leaving solid deposits.

Example 2

900 g of cyclohexane, 50 g of N-vinylimidazole, 50 g of N-vinylpyrrolidone and 5 g of divinylethylene urea were placed in a 1000 ml flask equipped with a stirrer, reflux condenser, thermometer and apparatus for working under protective gas and 1 g of tert-butyl perpivalate are heated to 80 ° C. with stirring. The mixture was stirred at this temperature for 5 hours. Subsequently, 595 g of a C ₃ / Cιs oxo alcohol, which had been reacted with 7 units of ethylene oxide per molecule, were added dropwise over the course of 1 hour and, at the same time, the cyclohexane was distilled off over a distillation bridge in a weak stream of nitrogen. A finely divided polymer suspension with an average particle size of 18.1 μ was obtained. Example 3

400 ml of a polyoxyethylene sorbitan stearate, 100 g of N-vinylpyrrolidone, 8 g of divinylethylene urea and 1 g were placed in a 1000 ml flask equipped with a stirrer, reflux condenser, thermometer and apparatus for working under protective gas tert-Amylperneodecanoat stirred at 72 ° C for 6 hours. A finely divided polymer suspension with an average particle size of 12.4 μm was obtained.

Example 4

In a 1000 ml flask equipped with a stirrer, reflux condenser, thermometer and an apparatus for working under protective gas, 400 g sorbitan monolate, 100 g vinyl imidazole and 2 g allyl methacrylate were heated to 80 ° C. At this temperature, a feed of 1 g of 2,2'-azobis (2-methylisobutyronitrile) in 50 ml of sorbitan monolaurate was added over a period of 4 hours. The reaction mixture was left at 80 ° C for a further 2 hours. A finely divided polymer suspension with an average particle size of 17.2 μm was obtained.

Example 5

800 g of cyclohexane, 5 g of sorbitan monolaurate and 5 g of an ABA block copolymer made of polyhydroxystearic acid and polyethylene oxide were added to a 2000 ml flask equipped with a stirrer, reflux condenser, thermometer and apparatus for working under protective gas a molecular weight of about 7500, sold by the company ICI under the

Name Hypermer B 246, heated to 65 ° C. As soon as this temperature was reached, a feed of 100 g of N-vinylpyrrolidone, 100 g of vinylimidazole, 10 g of divinylethylene urea and 0.5 g of 2,2'-azobis (amidinopropane) dihydrochloride in 140 g of water was added dropwise over 30 minutes. The mixture was then stirred at this temperature for a further 6 hours. The temperature was then raised until the mixture boiled and the water was distilled off azeotropically from the reaction mixture using a water separator. Subsequently, 800 g of a Cs / Cio-alkyl polyglycoside were added dropwise over the course of one hour and at the same time the cyclohexane was distilled off in a weak nitrogen stream via a distillation bridge. A finely divided polymer suspension with an average particle size of 7.3 μm was obtained. Application engineering examples

Test method

White cotton test fabric was washed under the washing conditions mentioned in Table 1 and with the addition of the detergent according to Table 2 in the presence of dye. The dye was detached from cotton test dyeings during the washing process.

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, Öle, 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.

Table 1: Washing conditions

Launder-O-meter device

Cycles 1

Duration 30 min

Temperature 60 ° C

Water hardness 3 mmol / 1 dye input dye fabric

Test fabric 2.5 g cotton nettle (bleached)

Amount of liquor 250 ml

Detergent concentration 4.5 g / 1 Table 2:

Detergent composition

Ingredients amount [%]

Linear Cιo / Ci3-alkylbenzenesulfonate Na salt

(50%) 8, 6

Fatty alcohol sulfate Na salt 2, 7

Addition product of 10 moles of ethylene oxide with 1 mole of C ₃ / Ci ₅ -oxoalcohol 6, 3

Zeolite A 5f

Na citrate 5.5 H ₂ 0 9.0

Copolymer of 70 wt .-% acrylic acid and

30% by weight of maleic acid, molar mass 70,000 4.0 Na carbonate 6.0

Na sulfate 5, 8

Carboxymethyl cellulose 0 5

Test substance 1 0

The washing results with the polymers according to the invention are shown in Table 3.

Table 3

The washing results in Table 3 show that the polymers according to the invention have very good activity as color transfer inhibitors and in many cases clearly exceeded the color transfer inhibitors polyvinylpyrrolidone or polyvinylpyrrolidone-covinylimidazole (comparative example 2) used in detergents. The results also show that the dye transfer inhibiting effect occurs with many direct dyes and is not restricted to individual representatives.

Claims

claims

1. Mixtures of polymers and surfactants, characterized in that they comprise 1 to 50% by weight of a polymer

a) 10 to 100 wt .-% of at least one vinylimidazole of the formula

R ^l

H ₂ C = CH N "^ N t ¹⁾ '* ² R ³

in which R ⁴ and R ^{5 are} identical or different and represent H, Ci to C ₄ alkyl or form a ring from 3 to 5 methylene groups with one another,

contained in suspended form.

2. Mixtures according to claim 1, characterized in that they are obtainable by radical-initiated polymerization of a ⁾ 10 to 100 wt .-% of at least one vinylimidazole of the formula

Ri

H ₂ C = CH "^ N (I),

Y ^ R ³

H ₂ C = CH NCR ⁵ (III

R ⁴

in which 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,

b) 0 to 90% by weight of other copolymerizable mono-ethylenically unsaturated monomers and

in at least one surfactant.

3. Mixtures according to claim 1, characterized in that the polymers

(a) N-vinylimidazoles of the formula (I), N-vinylpyrrolidone or mixtures of these monomers and (c) at least one monomer with at least two ethylenically unsaturated, non-conjugated double bonds

polymerized included. 23

4. Mixtures according to claim 2, characterized in that they are obtainable by polymerizing

(a) N-vinylimidazoles of the formula I, N-vinylpyrrolidone or mixtures of these monomers and

(c) at least one monomer with at least two ethylenically unsaturated, non-conjugated double bonds

in at least one nonionic surfactant.

5. Mixtures according to claim 2, characterized in that they are obtainable by polymerizing

(a) N-vinylimidazoles of the formula I, N-vinylpyrrolidone or mixtures of these monomers and (c) at least one monomer with at least two ethylenically unsaturated, non-conjugated double bonds

in at least one alcohol alkoxylated with ethylene oxide and / or propylene oxide.

6. A process for the preparation of the mixtures according to claim 1, characterized in that

(a) 10 to 100% by weight of at least one vinylimidazole of the formula

R ¹

H ₂ C = CH N ^^ (I)

^' R ³

in which R1, R2 and R3 are the same or different and stand for H, Ci to C alkyl,

Monomers of the formula

0

H ₂ C = CH N c R ^{5 (II)} '

R ⁴ in which R ⁴ and R ^{5 are} identical or different and represent H, Ci to C ₄ alkyl or form a ring from 3 to 5 methylene groups with one another,

(b) 0 to 90% by weight of other copolymerizable mono-ethylenically unsaturated monomers and

(c) 0 to 30% by weight of at least one monomer with at least two non-conjugated, ethylenically unsaturated double bonds

radically polymerized in at least one surfactant at temperatures of at least 50 ° C or that the monomers (a) and optionally (b) and / or optionally (c) are radically polymerized in the aqueous phase of a water-in-oil suspension and after completion the polymerization, the oil phase of the water-in-oil suspension is replaced by at least one surfactant.

7. Use of the mixtures according to claim 1 as an additive to detergents.