CA2219071A1 - Polymer and surfactant mixtures, process for their preparation and their use - Google Patents

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, the preparation thereof and the use thereof 5 The invention relates to mixtures of polymers of vinylim;AA7oles, vinylpyrrolidone, open-chain vinylAm;A~s, N-vinyloxazolidone or N-vinyltriazole, with or without other copolymerizable monoethylenically unsaturated monomers and with or without monomers having at least 2 non-conjugated ethylenic double bonds 10 and surfactants, to a process for preparing the mixtures and to the use of the mixtures as additive to detergents.
Polymers of l-vinylimidazole are prepared, for example, by free-radical polymerization of l-vinylimidazole in aqueous 15 solution or in alcohols, cf. DE-A-28 14 287. In order to prepare high molecular weight or crossl;nkeA polymers of l-vinyl;~;AA7ole it is possible to carry out precipitation polymerization in benzene, cf. EP-A-0 162 388. In addition, European Polymer Journal, 24 (1988) 1019 discloses the precipitation 20 polymerization of l-vinyl; m; AA7ole in carbon tetrachloride, benzene or toluene. However, the polyvinyl; ;AA7oles prepared in carbon tetrachloride have only low molecular weights, whereas the polymers prepared in benzene or toluene result as crossl;nkeA
gels.
WO-A-92/07011 discloses the preparation of polyvinylpyrrolidones which are slightly crossl;nk~A and highly swellable by polymerizing N-vinylpyrrolidone in, for example, aliphatic hydrocarbons. The polymers obtA;nAhle in this way are isolated by 30 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 objectionable or very flAmm~hle The resulting polymers have to be isolated from these solvents and, in some cases, undergo elaborate 35 purification.
It is an object of the present invention to provide polymers in a formulation which can be used directly and without isolating the polymers. It is also an object of the invention to develop a 40 process for preparing polymers contA;n;ng ; ;A~7ole and/or lactam groups which dispenses with the use of toxicologically objectionable solvents.
we have found that this object is achieved by mixtures of 45 polymers and surfactants when they contain from 1 to 50~ by weight of a polymer of .. . .

a) lO-100% by weight of at least one vinyl;m;~A7.ole of the formula Rl .
H2C = CH N ~ N (I), R2 ~ R3 where Rl, R2 and R3 are identical or different and are H, C l-C4-alkyl, monomers of the formula O

~2C = CH - I - C - R5 (II), where R4 and R5 are identical or different and are H, C1-C4-alkyl or together form a ring of 3 to 5 methylene groups, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide or mixtures of said monomers, b) 0-90% by weight of other copolymerizable monoethylenically unsaturated monomers and c) 0-30% by weight of at least one monomer having at least two non-conjugated ethylenic double bonds, in suspended form in at least one surfactant.
The invention also relates to a process for preparing the mixtures by free-radical polymerization of a) lO-100% by weight of at least one vinyl; ;~ole of the formula .. . .

H2C = CH - N ~ N (I), ~

where R1, R2 and R3 are identical or different and are H, Cl-C4-alkyl, monomers of the formula H2C = CH - N - C - R5 (II), where R4 and R5 are identical or different and are H, C1-C4-alkyl or together form a ring of 3 to 5 methylene groups, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide or mixtures of said monomers, 25 b) 0-90% by weight of other copolymerizable monoethylenically unsaturated monomers and c) 0-30% by weight of at leàst one monomer having at least two non-conjugated ethylenic double bonds, in at least one surfactant at not below 50~C, or comprises free-radical polymerization of the monomers (a) with or without (b) and/or with or without (c) in the aqueous phase of a water-in-oil suspension and, after completion of the 35 polymerization, replacing the oil phsae of the water-in-oil suspension by at least one surfactant.
Examples of monomers of form~llA I are 1-vinylimidazole, 2-methyl-1-vinyl; ;~A7ole, 2-ethyl-l-vinyl;m;t.~A7.ole, 40 2-propyl-1-vinyl; ;t.~A~ole, 2-butyl-l-vinyl;m;~zole~
2,4-dimethyl-1-vinylimidazole, 2,5-dimethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinyl;~;~A~ole, 2-ethyl-5-methyl-1-vinylimidazole, 2,4,5-trimethyl-1-viny~ A7ole, 4,5-diethyl-2-methyl-1-vinylimidazole, 4-methyl-1-vinyl;m;,.~A~ole, 45 5-methyl-1-vinylimidazole, 4-ethyl-1-viny~ A7ole, 4,5-dimethyl-1-viny~ A7ole or 2,4,5-triethyl-1-vinyli ;~A7ole.
Mixtures of said monomers in any desired ratio can be used.

, Monomers of formula II are open-chain and cyclic N-vinylAmi~.c, eg. N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone, N-vinylpiperidone or N-vinylcaprolactam. Of the compounds of the formula II, 5 preferably N-vinylpyrrolidone is used to prepare the mixtures according to the invention.
Particularly preferred monomers of group a) are l-vinyl;m;~A~ole, l-vinyl-2-methyl;m;~Azole or l-vinylpyrrolidone, and mixtures of 10 said monomers in any desired ratio. The polymers contain at least 10% by weight of monom~rs a) as copolymerized units. Monomers a) are used in amounts of from 10 to 100, preferably 50 to 100, in particular 85 to 99.5% of the total weight of the monomers used in the polymerization.
Suitable monomers of group b) are other monoethylenically unsaturated monomers which are copolymerizable with monomers of group a). Examples of such monomers are (meth)acrylates such as methyl, ethyl, hydroxyethyl, propyl, hydroxypropyl, butyl, 20 ethylhexyl, decyl, lauryl, isobornyl, cetyl, palmityl, phenoxyethyl or stearyl acrylate or the corresponding methacrylates, (meth)acrylamides such as acrylamide, N-methylolacrylamide, NrN-dimethyl Am; nQpropylacrylamide, N,N-diethylaminopropylacrylamide, N-tert-butylacrylAm;~
25 N-tert-octylacrylamide, N-undecylacrylAmi~e or the corresponding methacrylamides, vinyl esters having 2 to 30, in particular 2 to 14, carbon atoms in the molecule, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl neooctanoate, vinyl neononanoate, vinyl neodecanoate, styrene, vinyltoluene, 30 a-methylstyrene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or the corresponding anhydrides, 2-acryl A ; ~o-2-methylpropanesulfonic acid, acrylic esters which have a basic nitrogen atom, such as diethylAm;noethyl acrylate, 35 dimethylaminoethyl acrylate, dimethylAm;nopropyl acrylate or the corresponding methacrylates, 2-vinylpyridine or 4-vinylpyridine.
Alkyl (meth)acrylates, vinyl acetate, styrene, acrylic acid, methacrylic acid, maleic acid and monomers which have a basic nitrogen atom are particularly preferred.
If monomers b) are used, they are present in amounts of up to 90, preferably up to 50, % of the total weight of all the monomers.
Suitable monomers of group c) are compounds having at least 2 45 non-conjugated ethylenic double bonds in the molecule. Compounds of this type are crosslinkers. Examples of suitable crossl;nkr~rs are acrylates, methacrylates, allyl ethers or vinyl ethers of at OO~O/45899 CA 02219071 1997-11-14 least dihydric alcohols. The OH groups in the underlying alcohols can be wholly or partly etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups. Examples of the underlying alcohols are dihydric alcohols 5 such as 1,2-et h~ ne-l;ol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-h~ne~;ol, 1,10-dec~neA;ol, 1,2-dodec~ne~;ol, 1,12-dodecanediol, neopentyl glycol, lO 3-methyl-1,5-pent~ne~;ol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cycloh~ne~;ol, 1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexAne, neopentyl glycol mono(hydroxypivalate), 2,2-bis(4-hydroxyphenyl)propane, 2,2-bist4-(2-hydroxypropyl)phenyl]propane, diethylene glycol, 15 triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thia-1,5-pentanediol, and polyethylene glycols, polypropylene glycols and polytetrahydrofurans having molecular weights of, in each case, from 200 to 10,000. Apart from homopolymers of 20 ethylene oxide or propylene oxide, it is also possible to use block copolymers of ethylene oxide or propylene oxide or copolymers which contain ethylene oxide and propylene oxide groups incorporated. Examples of underlying alcohols having more than two OH groups are trimethylolpropane, glycerol, 25 pentaerythritol, 1,2,5-pentanetriol, 1,2,6-he~netriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose. It is, of course, also possible for the polyhydric alcohols to be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene 30 oxide. The polyhydric alcohols can also be initially converted into the corresponding glycidyl ethers by reaction with epichlorohydrin.
Further suitable crossl;nkers are the vinyl esters or the esters 35 of monohydric unsaturated alcohols with ethylenically unsaturated C3-C6-carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 40 10-undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. However, it is also possible for the monohydric unsaturated alcohols to be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid 45 or succinic acid.

Further suitable crossl; nk~r5 are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example of oleic acid, crotonic acid, c;nnAm;c 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, in the case of aliphatic hydrocarbons, must not be conjugated, eg. divinylbenzene, divinyltoluene, 1,7-octadiene, 10 l,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200-20,000. Also suitable as crosslinkers are the acrylamides and methacrylAm;r~r~s of at least difunctional amines. Examples of such Am;neS are diaminomethane, 1,2-dir ;noethane, 1~3-~; ~m; nopropane, 15 1,4-~;Am;nohutane, 1,6-~;Am;nohe~Ane, 1,12-dodecaner1;Am;nQ, piperazine, diethylenetr;Am;ne or isophoronediamine. Also suitable are the amides from allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids as 20 described above.
Also suitable are N-vinyl compounds of urea derivatives, at least difunctional amides, cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartaramide.
Further suitable crosslinkers are divinyl~;o~Ane, tetraallylsilane or tetravinylsilane. It is, of course, also possible to use mixtures of the abov~ ~ntioned compounds. The crosslinkers which are preferably used are those which are 30 soluble in the reaction mixture. Particularly preferred crosslinkers are methylenebisacrylamide, di- and triallyl~m;ne, divinylimidazole, divinylethyleneurea, products of the reaction of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylates and acrylates of polyalkylene oxides or of 35 polyhydric alcohols which have been reacted with ethylene oxide and/or propylene oxide and/or epichlorohydrin, and allyl methacrylate and divinylbenzene. Methylenebisacrylamide, N,N'-divinylethyleneurea, acrylates and methacrylates of at least dihydric C2-C4-alcohols, allyl methacrylate and divinylbenzene are 40 very particularly preferred. If crossl;nk~s are used in the polymerization, they can be employed in amounts of up to 30, preferably from 0.2 to 20, and very particularly preferably from 0.5 to 10, % of the total weight of monomers used in the polymerization.

: 7 The mixtures according to the invention comprise 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 5 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 10 acyclic, aromatic or aliphatic alkyl radical having 8 to 40, preferably 10 to 30, very particularly preferably 12 to 22, carbon atoms in the molecule. The alkyl r~; CA 1 can also be wholly or partly fluorinated. The alkyl radical is linked to a hydrophilic moiety which contains at least one oxygen or nitrogen 15 atom. Examples of preferred compounds are 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 alkanolamides such 20 as fatty acid ethanolamides, fatty acid isopropanolamides, fatty acid diethanolamides, fatty acid polydiethanolamides, N-alkylpyrrolidone derivatives, alkyl pyrrolidone-5-carboxylates, citric and tartaric esters, Cl-Cl8-alkyl (poly)glycosides, hydroxyalkyl polyglycosides, fatty acid esters of polyhydroxy 25 compounds such as trimethylolpropane, erythritol, pentaerythritol, neopentyl diglycol, triethanolamine or condensates derived therefrom, alkoxylates, especially the adducts of ethylene oxide and/or propylene oxide with the abo~t -ntioned compounds and with oxo alcohols, C8-C30-alcohols, 30 alkylphenols, fatty acid ~m;~es, fatty amines, fatty acids and derivatives such as hydroxy carboxylic acids, it being possible for the polyalkylene oxide ch~; n~ to be modified at one end or both ends. In the case of modification at both ends, the modifying portions can be identical or different and, for 35 example, also represent in part a C1-C4-ether functionality.
Further surface-active compounds a) are sorbitan esters, sucrose esters or glycerol esters of C8-C30-carboxylic acids or alkoxylation products of these esters. The abo~ ~ntioned esters 40 are preferably derived from Cl2-C22-carboxylic acids. Alkoxylation products are preferably the adducts of ethylene oxide with the esters. The adducts may contain up to 80 mol of ethylene oxide per mol of the relevant esters. Also suitable as surface-active compounds are adducts of ethylene oxide and propylene oxide 45 and/or of butylene oxides with the esters. Alkyldimethylamine oxides are likewise suitable.

0050/4~899 CA 022l907l l997-ll-l4 r 8 Polymeric surfactants which contain ethylene oxide and/or propylene oxide units as hydrophilic part of the molecule are not crosslinked and have molecular weights of from 500 to 100,000, preferably 700 to 20,000. The polymeric surfactants may, besides 5 at least one hydrophilic block, contain at least one hydrophobic block or are composed of a hydrophilic chain with hydrophobic branches arranged like a comb. The hydroph;l;c part of the polymeric surfactants is formed from homopolymers of ethylene oxide or propylene oxide or from block copolymers of ethylene lO oxide and propylene oxide and from block and comb polymers with blocks of polyethylene oxide, polypropylene oxide or poly co(ethylene oxide, propylene oxide), while the hydrophobic part of the polymeric surfactants consists of blocks of polysLylene polyalkyl (meth)acrylates, silicone oils, polyhydLoxy fatty 15 acids, polyamidoamines, polyisobutylene or polytetrahydrofurans.
It is also possible for general polymers which have at least one amino group, one hydroxyl group which can be deprotonated with bases, or one anionic group, and have a molecular weight of from 100 to 5000, such as ethylene oxide, propylene oxide or mixtures 20 thereof, to be converted into suitable polymeric surfactants.
Particularly preferred surfactants among those mentioned above are adducts of ethylene oxide and/or propylene oxide with Cl0-C30-alcohols, alkylphenols, fatty ~m; neC or fatty acids, 25 sucrose esters, sorbitan esters, (poly)glycerol esters or their corresponding ethoxylates, and alkyl (poly)glycosides. Adducts of ethylene oxide and/or propylene oxide with C12-C22-alcohols or alkylphenols, sorbitan esters, glycerol esters or their corresponding ethoxylates with 12 to 22 carbon atoms in the alkyl 30 chain, and alkyl (poly)glycosides with 8 to 22 carbon atoms in the alkyl chain, are very particularly preferred. The surfactants have, for example, a softening point below 100 C, preferably below 60~C and particularly preferably below 40~C.
35 Polymers of monomers a) with or without b) and/or with or without c) are known. They can be prepared by various processes.
Particularly suitable processes are inverse suspension or emulslon polymerization, where an aqueous solution of the monomers is emulsified in an inert organic liquid and 40 polymerized, and precipitation polymerization. It is possible and expedient in water-in-oil polymerization to use protective colloids or emulsifiers. After the polymerization is complete, the water can be removed, for example by azeotropic distillation, and the inert organic solvent can be replaced by a nonionic 45 surfactant by, for example, l~ ~ving the inert organic solvent by t distillation and preferably adding an amount of surfactants which corresponds to the amount L~ ~ved by distillation.
The solvents used in precipitation polymerization are those which 5 dissolve the monomers, at least in part, but not the polymers resulting therefrom, so that they precipitate in fine-particle form. Examples of solvents suitable for water-in-oil emulsion polymerization are saturated, straight-chain or branched or cyclic hydrocarbons such as pentane, h~ne~ cyclohexane, 10 heptane, octane or isooctane, ~l;ph~tic ethers such as dimethyl ether, diethyl ether, diamyl ether, tert-butyl methyl ether or dibutyl ether, ketones such as acetone, methyl ethyl ketone, diethyl ketone or methyl amyl ketone, Cl-C18-carboxylic esters, for example ethyl formate, methyl acetate, ethyl acetate, 15 isopropyl acetate, isobutyl acetate, stearyl acetate, ethylhexyl ethylhexanoate, isopropyl myristate or isopropyl palmitate, silicone oils such as octamethylcyclotetrasilane, liquid or supercritical carbon dioxide, aromatic hydrocarbons such as toluene or xylene. These inert organic solvents are substantially 20 replaced by a surfactant after the polymerization.
The mixtures are preferably obt~;n~hle by free-radical polymerization of 25 a) 10-100% by weight of at least one vinyl; ;~ole of the formula .

Rl H2C = CH--N~W (I), where Rl, R2 and R3 are identical or different and are H, Cl--C4-alkyl, monomers of the formula O
H2C = CH I - C - R5 (II), OO~O/45899 CA 02219071 1997-11-14 where R4 and R5 are identical or different and are H, Cl-C4-alkyl or together form a ring of 3 to 5 methylene groups, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide or mixtures of said monomers, b) 0-90% by weight of other copolymerizable monoethylenically unsaturated monomers and 10 c) 0-30% by weight of at least one monomer having at least two non-conjugated ethylenic double bonds, in at least one surfactant.
15 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 desired ratio, with the solvent being removed as completely as possible from the reaction mixture following the polymerization. The amount of the organic phase 20 during the polymerization is preferably chosen 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.
It is also possible to add 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 to the reaction mixture in order to improve the 30 solubility of individual components of the reaction mixture or in order to influence the properties of the resulting copolymers.
For example, the morphology of the polymers can be infuenced in the presence of protective colloids in such a way that the resulting mixtures have a particularly high polymer content.
35 Examples of suitable protective colloids are polyvinylpyrrolidones with K values of from 10 to 100, partially hydrolyzed polyvinyl acetates, cellulose ethers, copolymers of maleic acid or maleic anhydride with alkenes, preferably isobutylene or diisobutylene, or copolymers of N-pyrrolidone and 40 vinyl acetate. If water is present in the precipitation polymerization, it is used only in the amounts needed to make the mixture of all the components appear homogeneous before the start of the polymerization.
45 The molecular weight of the resulting polymers can, where appropriate, be reduced by adding regulators to the polymerizing mixture. Examples of regulators which can be used are halogen t compounds such as tetrachloromethane, chloroform, bromotrichloromethane, allyl compounds such as allyl alcohol or 2,5-diphenyl-1-hexene, aldehydes, formic acid or formic esters.
However, the polymerization regulators preferably used are 5 compounds which contain sulfur in bound form, for example bisulfites, sulfites, disulfites and dithionites or compounds which contain sulfur l;nke~ to a carbon atom, such as organic sulfides, disulfides, polysulfides, sulfoxides, sulfones and mercapto compounds. Particularly preferably used are mercapto 10 alcohols, mercapto carboxylic acids and mercaptoalkanes having 2 to 30 carbon atoms in the molecule, for example 2-mercaptoethanol, 3-mercaptopropanol, 3-mercapto-1,2-propanediol, 4-mercaptobutanol, cysteine, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic 15 acid, N-butyl mercaptan, N-hexyl mercaptan, N-dodecyl mercaptan or tert-dodecyl mercaptan. If polymerization regulators are used, they are employed in amounts of from 0.1 to 10, preferably 0.1 to 5, % of the weight of monomers in the reaction mixture.
20 The abo~.entioned monomers are normally polymerized with use of free-radical initiators, as a rule under an inert gas atmosphere.
Free-radical initiators which can be used are hydrogen peroxide or inorganic persulfates, as well as organic compounds of the peroxide, peroxy ester, percarbonate or azo type, such as 25 dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl perpivalate, t-amyl perpivalate, t-butyl perneo~c~noate, 2,2~-azobis(2-amidinopropane) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2~-azobis~2-(2-;mi~olin-2-yl)propane] dihydrochloride, 30 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) and dimethyl 2,2'-azobis(isobutyrate). It is, of course, also possible to use mixtures of initiators or the known redox initiators. The initiators which are preferably used are those 3S which, when the polymerization is carried out in surfactants, are soluble in the surfactants to the extent of more than 5% by weight at 25 C. The initiators are used in conventional quantities, eg. from 0.02 to 5% of the weight of monomers to be polymerizedO
The precipitation polymerization is norr~lly carried out under an inert gas atmosphere. The polymerization can be carried out, for example, by introducing all the components which are present during the polymerization into a polymerization vessel, starting 45 the reaction, and cooling the reaction mixture where appropriate to control the polymerization temr~ature. However, it is also possible to introduce only one or some of the components, to , r start the polymerization, and to meter the rr~-;n~r of the components in singly or together at different intervals depending on the progress of the polymerization, continuously or batchwise.
However, it is also possible to introduce first only the diluent S and to add the monomers and the polymerization initiator in separate feeds thereto, batchwise or continuously.
The monomers are generally polymerized at from 40 to 200, preferably 50 to 120, C. The temperature can be varied during the 10 reaction in a program-controlled ~nn~r. The polymerization is preferably carried out under atmospheric pressure, but can also be carried out under reduced or elevated pressure. If the polymerization is carried out above the boiling point of the solvent, pressure-tight apparatus with pressures of up to 16 bar 15 is used.
In the preparation of crosslinked copolymers, it is well known that there is often formation of deposits, which are difficult to remove, on the walls of the reaction vessels and on the stirrers.
Z0 In the preparation according to the invention of the mixtures by copolymerization of the monomers in, preferably, nonionic surfactants as precipitant there is virtually none of the otherwise unwanted deposit formation.
25 Polymers which (formally) contain 4-vinylpyridine N-oxide as copolymerized unit are preferably prepared by polymerization or copolymerization of 4-vinylpyridine followed by N-oxidation of the pyridine ring with, for example, peracetic acid prepared in situ.
Polymers which have basic, N-cont~ining groups can be converted after the reaction into a quaternized form with a suitable reagent. Examples suitable for the quaternization are alkyl halides having 1 to 18 carbon atoms in the molecule, eg. methyl 35 chloride, ethyl chloride, propyl chloride, hexyl chloride, dodecyl chloride or lauryl chloride, and benzyl halides such as benzyl chloride. The corresponding iodine or bromine compounds are, of course, also suitable. Further suitable quaternizing agents are dialkyl sulfates, in particular dimethyl sulfate and 40 diethyl sulfate. In some cases, it is sufficient to convert the polymers into the salt form by treatment with an acid. The quaternization can take place completely or partially.
The reaction mixture can be subjected after the polymerization to 45 a physical or ch~ical treatment. Examples thereof are the known processes for reducing residual monomers, such as addition of polymerization initiators or mixtures of a plurality of ~ F

polymerization initiators at suitable temperatures or heating of the polymerization solution to temperatures above the polymerization temperature, treatment of the polymer solution with steam or stripping with nitrogen or treatment of the 5 reaction mixture with oxidizing or reducing reagents.
If the polymers are soluble in water, they have K values of from lO to 300 (determined by the method of H. Fikentscher in aqueous solution at 25 C with a polymer concentration of 1%~. The average 10 diameter of the polymers is, for example, from 0.1 to 1000, preferably 0.5 to 80, ~m.
The suspensions according to the invention of the copolymers in the surfactants are used, for example, as additive for 15 ph~r~Aceutical or cosmetic compositions, as additive in paper manufacture, for stabilizing enzymes or for adsorbing metal ions, dyes or acids. The particularly preferred use is as additive to detergents. The effect of the polymers in the washing of colored and white textiles is to inhibit transfer of dye to the uncolored 20 textiles.
In particular, crosslinked copolymers of N-viny~ zole and N-vinylpyrrolidone are particularly suitable for use in heavy duty detergents because they are distinctly more effective than 25 soluble polymers when the dye co~centrations in the wash li~uor are low. However, as a rule, in the full wash it is mainly white and slightly colored l~lln~ry, and lA~ln~ry with very washfast colors, which is washed. T~nn~ry which releases dye to a large extent is, as a rule, present in the lAlln~ry only by mistake and 30 thus as a very small proportion, eg. when a colored sock is included in the wash. The crosslinked polymers, which bind small amounts of dye distinctly more strongly than do 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 in a liquid formulation.
The composition of the detergents and cleaners may vary widely.
Detergent and cleaner fo l~tions nor~lly contain from 2 to 50%
by weight of surfactants, with or without bn;l~rs . These data 40 apply both to li~uid and to powder detergents. Detergent and cleaner formulations, c~ -nly used in Europe, the USA and Japan are tabulated, for example, in Chemical and Engn. News, 67 (1989) 35. Further details of the composition of detergents and cleaners can be found in Ull~-nn~ Enzyklopadie der technischen Chemie, 45 Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160. The detergents may also contain a bleach, eg. sodium perborate or sodium percarbonate, whose content when used can be up to 30% of , the weight of the detergent formulation. The detergents or cleaners may contain further conventional additives, eg.
complexing agents, opacifying agents, optical brighteners, enzymes, perfume oils, other color transfer inhibitors, 5 antiredeposition agents, soil release polymers and/or bleach activators. They contain the mixtures according to the invention in amounts of from 0.1 to 10, preferably 0.2 to 3, % by weight.
Examples Example 1 440 g of a Cl3/Cl5 oxo alcohol which had been reacted with 7 units of ethylene oxide per molecule were heated with 50 g of 15 N-vinyl;~;~ole, 50 g of N-vinylpyrrolidone, 5 g of divinylethyleneurea and 1 g of tert-butyl perpivalate while stirring in a flask which had a capacity of 2000 ml and was equipped with a stirrer, reflux condenser, thermometer and apparatus for working under protective gas, to 80~C. The mixture 20 was stirred at this t~mr~rature for 5 hours. The result was a fine-particle, white polymer suspension with an average particle size of 14.3 ~m. The suspension was easy to pour out of the polymerization vessel without leaving solid deposits behind.
25 Example 2 900 g of cyclohexane, 50 g of N-vinylimidazole, 50 g of N-- vinylpyrrolidone, 5 g of divinylethyleneurea and 1 g of tert-butyl perpivalate were heated in a flask which had a 30 capacity of 1000 ml and was equipped with a stirrer, reflux condenser, thermometer and an apparatus for working under protective gas while stirring to 80~C. The mixture was stirred at this temperature for 5 hours. Subsequently 595 g of a Cl3/Cl5 oxo alcohol which had been reacted with 7 units of ethylene oxide per 35 molecule were added dropwise over the course of 1 hour and, at the same time, the cyclohexane was lel..oved by distillation under a gentle stream of nitrogen. The result was a fine-particle polymer suspension with an average particle size of 18.1 ~m.
40 Example 3 400 ml of a polyoxyethylene sorbitan stearate, 100 g of N-- vinylpyrrolidone, 8 g of divinylethyleneurea and 1 g of tert-amyl perneodecanoate were stirred in a flask which had a 45 capacity of 1000 ml and was equipped with a stirrer, reflux condenser, th~ -ter and an apparatus for working under OO~O/45899 CA 02219071 1997-11-14 protective gas at 72 C for 6 hours. The result was a fine-particle polymer suspension with an average particle size of 12.4 ~m.
Example 4 400 g of sorbitan monolaurate, 100 g of vinylimidazole and 2 g of allyl methacrylate were heated to 80 C in a flask which had a capacity of 1000 ml and was equipped with a stirrer, reflux condenser, thel -Ler and an apparatus for working under lO protective gas. At this temperature, 1 g of 2,2'-azobis(2-methylisobutyronitrile) in 50 ml of sorbitan monolaurate was fed in over the course of 4 hours. The reaction mixture was left at 80 C for a further 2 hours. The result was a fine-particle polymer suspension with an average particle size of 15 17.2 ~m.
Example 5 800 g of cyclohex~ne~ 5 g of sorbitan monolaurate and 5 g of an 20 ABA block copolymer of polyhydroxystearic acid and polyethylene oxide with a molecular weight of about 7500, marketed by ICI
under the name Hyp~ -r B 246, were heated to 65~C in a flask which had a capacity of 2000 ml and was equipped with a stirrer, reflux condenser, ther -Ler and an apparatus for working under 25 protective gas. As soon as this temperature was reached, 100 g of N-vinylpyrrolidone, 100 g of vinyl; ;A~ole, 10 g of divinylethyleneurea and 0.5 g of 2,2'-azobis(Am;Ainopropane) dihydrochloride in 140 g of water were added dropwise over the course of 30 minutes. The mixture was then stirred at this 30 temperature for a further 6 hours. The t~ ~rature was subsequently raised to the boiling point of the mixture, and the water was ,~,..oved by azeotropic distillation. Subsequently 800 g of a C8/C10-alkyl polyglycoside were added dropwise over the course of one hour and, at the same time, the cycloh~ne was 35 le,.loved by distillation under a gentle stream of nitrogen. The result was a fine-particle polymer suspension with an average particle size of 7.3 ~m.
Use Examples Test method White cotton test fabric was washed under the conditions specified in Table 1 with the addition of the detergent indicated 45 in Table 2 in the presence of dye. The dye was released during the washing from cotton test dyeings.

Table 1 contains the washing conditions for the examples. Table 2 indicates the composition of the detergents used. The coloring of the test fabric was measured by photometry. The strengths of each of the colorings were det~rm;ne~ by the method described by 5 A. Kud, Seifen, Ole, Fette, Wachse, 119 (1993) 590-594 from the reflectance measurements on the individual test fabrics. The color-transfer inhibiting effect of the test substance was determined as a % from the color strengths for the test with the particular test substance, the color strength for the test 10 without test substance and the color strength of the test fabric before washing by the method described in the above reference (color transfer inhibition is treated in the same way as antiredeposition for this purpose). The effectiveness results for the various dyes are listed in Table 3.
Table 1:
Washing conditions Machine T~lln~er-o-meter 20 Cycles Duration 30 min Temperature 60 C
Water hardness 3 mmol/l Dye introduction Colored fabric 25 Test fabric 2.5 g of cotton cheesecloth (bleached) Amount of liquor 250 ml Detergent concentration 4.5 g/l 30 Table 2:
Detergent composition Ingredients Amount t~]
35 Linear Na C10/Cl3-alkylbenzenesulfonate (50% strength) 8.6 Na fatty alcohol sulfate 2.7 Adduct of 10 mol of ethylene oxide at 1 mol of Cl3/Cl5 oxo alcohol 6.3 40 Zeolite A 55 Na citrate 5.5 H20 9.0 Copolymer of 70% by weight acrylic acid and 30% by weight maleic acid, molecular weight 70,000 4.0 45 Na carbonate 6.0 Na sulfate 5.8 . . I ~

Carboxymethylcellulose 0.5 Test substance 1.0 The washing results with the polymers according to the invention 5 are shown in Table 3.

0050~45899CA 02219071 1997-11-14 Table 3 Direct Direct Direct blue black orange Mixture of Example 1 95.6 71.4 45.8 Mixture of Example 2 96.0 82.7 48.2 Comparative Example 1 10 (polyvinylpyrrolidone . 94.7 60.2 23.9 with K value of 30) Comparative Example 2 (1:1 vinylimidazole/
vinylpyrrolidone 94.1 60.4 28.7 copolymer with K value 15 ~f 18) The washing results in Table 3 show that the polymers according to the invention are very effective as color transfer inhibitors and are in many cases distinctly superior to the color transfer 20 inhibitors polyvinylpyrrolidone or polyvinylpyrrolidone-co-vinyl;mi~ole (Comparative Example 2) which are used in many detergents. The results also show that the color-transfer inhibiting effect operates with many direct dyes and is not confined to a few representatives.

Claims (7)

We claim:

1. A mixture of a polymer and a surfactant, which contains from 1 to 50% by weight of a polymer of a) 10-100% by weight of at least one vinylimidazole of the formula ( I ), where R1, R2 and R3 are identical or different and are H, C1-C4-alkyl, monomers of the formula ( II ), where R4 and R5 are identical or different and are H, C1-C4-alkyl or together form a ring of 3 to 5 methylene groups, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide or mixtures of said monomers, b) 0-90% by weight of other copolymerizable monoethylenically unsaturated monomers and c) 0-30% by weight of at least one monomer having at least two non-conjugated ethylenic double bonds, in suspended form.

2. A mixture as claimed in claim 1, which is obtainable by free-radical polymerization of a) 10-100% by weight of at least one vinylimidazole of the formula ( I ), where R1, R2 and R3 are identical or different and are H, C1-C4-alkyl, monomers of the formula ( II ), where R4 and R5 are identical or different and are H, C1-C4-alkyl or together form a ring of 3 to 5 methylene groups, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide or mixtures of said monomers, b) 0-90% by weight of other copolymerizable monoethylenically unsaturated monomers and c) 0-30% by weight of at least one monomer having at least two non-conjugated ethylenic double bonds, in at least one surfactant.

3. A mixture as claimed in claim 1, wherein the polymers contain (a) N-vinylimidazoles of the formula (I), N-vinylpyrrolidone or mixtures of these monomers and (c) at least one monomer with at least two non-conjugated ethylenic double bonds, as copolymerized units.

4. A mixture as claimed in claim 2, which is obtainable by polymerization of (a) N-vinylimidazoles of the formula (I), N-vinylpyrrolidone or mixtures of these monomers and (c) at least one monomer with at least two non-conjugated ethylenic double bonds, in at least one nonionic surfactant.

5. A mixture as claimed in claim 2, which is obtainable by polymerization of (a) N-vinylimidazoles of the formula (I), N-vinylpyrrolidone or mixtures of these monomers and (c) at least one monomer with at least two non-conjugated ethylenic double bonds, in at least one alcohol alkoxylated with ethylene oxide and/or propylene oxide.

6. A process for preparing a mixture as claimed in claim 1, which comprises free-radical polymerization of a) 10-100% by weight of at least one vinylimidazole of the formula (I), where R1, R2 and R3 are identical or different and are H, C1-C4-alkyl, monomers of the formula (II), where R4 and R5 are identical or different and are H, C1-C4-alkyl or together form a ring of 3 to 5 methylene groups, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide or mixtures of said monomers, b) 0-90% by weight of other copolymerizable monoethylenically unsaturated monomers and c) 0-30% by weight of at least one monomer having at least two non-conjugated ethylenic double bonds, in at least one surfactant at not below 50°C, or comprises free-radical polymerization of the monomers (a) with or without (b) and/or with or without (c) in the aqueous phase of a water-in-oil suspension and, after completion of the polymerization, replacing the oil phase of the water-in-oil suspension by at least one surfactant.

7. The use of a mixture as claimed in claim 1 as additive to detergents.