CA2081199A1 - Use of polymerizates containing n-(alkyloxy-polyalkoxymethyl)carbonamide groups as additives to washing and cleaning agents - Google Patents

Abstract

O.Z.0050/41782 Abstract of the Disclosure: Polymers which contain as essential monomer at least 5% by weight of N-(alkyloxy-polyalkoxymethyl) carboxamides of monoethylenically unsaturated C3-C8-carboxylic acids as copolymerized units are used as additives in low-phosphate and phosphate-free detergents in amounts which increase their primary and secondary detergency.

Description

2~119~
O.Z. 0050/41782 Use of_eolymers_with N-(alkyloxypolyalkox~nethyl!-carboxamide grouPS as detergent additives The present invention relates to the use of polymers containing as essential monomer N-(alkyloxypoly-alkoxymethyl)carboxamides of monoethylenically unsatura-ted C3-C8-carboxylic acids as copolymerized units as - detergent additives and detergents containing such polymers.
For ecological reasons the recent past has witnessed an intensified search for substances to take the place of phosphates in detergents. Particularly important phosphate replacements are the polymers described in EP-B-0 025 551. They comprise copolymers of maleic acid and acrylic acid and are used as incrustation inhibitors in detergents in amounts of up to 10% by weight of the detergent formulation. By means of these copolymers it is possible to replace the hitherto custo-mary phosphates in detergents in whole or in part. After the washing process, the copolymers pass into the waste-water and are almost completely absorbed therefrom in water treatment plants by the sewage sludge. However, liquid detergents containing copolymers of acrylic acid and maleic acid as phosphate substitutes frequently tend to separate on storage.
US-A-4 746 456 discloses using graft copolymers of vinyl acetate on polyalkylene glycols as grayness inhibitors in detergent formulations.
EP-~-l 116 930 discloses water-solublecopolymers of from 40 to 90% by weight of at least one ethylenically unsaturated monocarboxylic acid of from 3 to 5 carbon atoms and from 60 to lO~ by weight of at least one ethylenically unsaturated dicarboxylic acid of from 4 to 8 carbon atoms and/or the anhydride thereof, in which from 2 to 60% by weight, based on the total weight of the carboxylic acids or anhydrides, are esterified with alkoxylated C1-C18-alcohols or C1-C12~alkylphenols. The partially esterified copolymers and their water-soluble 2 0 ~
2 - O.Z. 0050/41782 salts are also used, inter alia, in liquid detergents in amounts of from 0.5 to 10~ by weight. As is known from this reference, the compatibility of the partially esterified copolymers of at least one monoethylenically unsaturated monocarboxylic acid and at least one mono-ethylenically unsaturated dicarboxylic acid is distinctly better than that of the non-esterified products, so that phase separation is less likely. However, the partially esterified copolymers of the type described are not stable to hydrolysis, so that they hydrolyze in liquid detergent formulations. This gives rise to inhomo-geneities which may even lead to phase separation of the liquid detergent.
EP-A-0 237 075 discloses liquid detergents which contain at least one nonionic surface-active agent in an amount of from 5 to 25~ by weight, from 2 to 25% by weight of a builder, about 1-10% by weight of C4-C30-~-olefin/maleic anhydride copolymers and water to 100~ by weight. It is true that these liquid detergents are initially clear solutions, but they separate rela-tively rapidly on storage.
US-A-3 328 309 discloses liquid alkaline deter-gent formulations which besides water and detergents contain as stabilizer from 0.1 to 5~ by weight, based on the entire formulation, of a hydrolysed copolymer of an ~ unsaturated carboxylic anhydride with a vinyl ester, vinyl ether or an ~-olefin in partially esterified form.
The possible esterifying alcohol components include inter alia addition products of alkylene oxides, in particular ethylene oxide, with alkyl phenols. Only from 0.01 to 5~
of the carboxyl groups of the copolymer are present in the ester form. It is true that these liquid detergents contain components which are compatible with one another, but the primary detergency of this li~uid detergent formulation is still in need of improvement.
EP-A-0 215 251 discloses the use of homopolymers of acrylic acid and methacrylic acid, copolymers of 2 ~ $ ~ e~
~ 3 ~ O. Z . 0050/41782 acrylic acid and methacrylic acid and of copolymers of ethylenically unsaturated dicarboxylic acids of from 4 to 6 carbon atoms and acrylic acid or methacrylic acid each partially neutralized and/or amidated with long-chain 5 amines as grayness inhibitors and primary detergency promoters in detergents in amounts of from 0. 05 to 10%
by weight. The partially amidated homopolymers and copolymers are prepared by reacting the polymers with long-chain amines. In many cases they still contain free amines, which are not desirable in detergent formulations because they smell and pose a health risk.
Furthermore, US-A-4 797 223 discloses copolymers of acrylic or methacrylic esters of ethoxylated alcohols for use as detergent additives. EP-A-0 368 214 discloses the use of copolymers of monoethylenically unsaturated C3-Ca-carboxylic acids, esters of these carboxylic acids with alkyl vinyl ethers or mixtures of these monomers and amides of monoethylenically unsaturated C3-C8-carboxylic acids, in which the amide groups contain a C8-Cz8-alkyl moiety or a polyalkyleneoxy moiety which is bonded to ~he nitrogen atom via an alkylene group as liquid detergent additives in amounts of up to 20% by weight. It is true that such copolymer~ make it possible to produce storable liquid detergents, but they hydrolyze relatively rapidly at the high detergent pH.
It iB an object of the present invention to provide a po:Lymer for use in detergents which is simple to prepare and stable to hydrolysis at high pH.
We have found that this object is achieved according to the present invention by using a polymer containing as essential monomer at least 5% by weight of N-(alkyloxypolyalkoxymethyl)carboxamides of monoethy-lenically unsaturated C3-C8-carboxylic acids having amide groups of the structure -CO-NH-CH2-R, (I) 2 ~
4 - O.z. 0050/41782 where R = Rl~}(cH--CH~) --, RI~CH2--CH2--CH2~) R1 = C1-C28-alkyl, C3-C28-alkenyl, phenyl or C1-C18-alkyl-phenyl, R2 and R3 are each H, CH3 or C2H5, n is from 1 to 200 and m is from 1 to 100 as copolymerized units, as an addition to low-phosphate and phosphate-free detergents in amounts which increase the primary and secondary detergency of these detergents.
The polymers to be used in detergents according to the present invention contain as the essential monomer at least 5~ by weight of N-(alkyloxypolyalkoxymethyl)car-boxamides of monoethylenically unsaturated C3-C8-car-boxylic acids having amide groups of the above-indicated structure I. Compounds of this structure are obtainable by the method of Example 11 of EP-B-0 063 018 by reacting N-isobutoxymethylacrylamide with alkoxylated alcohols in the presence of acids. Instead of polyalkoxylated alco~
hols it is also possible to use the reaction products of alcohols and polytetrahydrofuran. Such reaction products can be characterised by means of the formula II:
R1-O-(CH2-CHz-CH2-CH2-O)m-H (II), where Rl is C2-C28-alkyl, C3-C28-alkenyl, phenyl or C1-C18-a:Lkylphenyl and m is from 1 to 100, preferably from 3 to 70.
Compounds of structure I are preferably obtained by reacting N-(C1-C4-alkyloxymethyl)carboxamides of ethylenically unsaturated C3-C8-carboxylic acids with alkoxylated compounds of the following formulae:

R2 R3 (III), where R1is C1-C28-alkyl, C3-C28-alkenyl, phenyl or C1-C18-alkylphenyl~
R2 and R3 are each hydrogen, methyl or ethyl, and 2 ~ 8 ~
5 - o.z. 0050/41782 n is from 1 to 200, preferably from 3 to 100.
Compounds of th0 formula III are obtained in the [sic] reacting monohydric C1-C28-alcohols, monohydric C3-C28-alkenols, phenol or C1-C18-alkylphenols with alkylene oxides of 2-4 carbon atoms. The OH-containing compounds mentioned can be reacted for example with ethylene oxide, propylene oxide or butylene oxide. The alkylene oxides can be used in the alkoxylation reaction either alone or - mixed~ If the latter, the alkoxylation products will contain the alkylene oxides as copolymerized units in random distribution. Howe~er, the alkylene oxides can also be used in the alkoxylation reaction in succession, which produces block copolymers. For instance, a compound of the formula Rl-O-H, where R1 is as defined for the formula III, i5 reacted first with ethylene oxide, then with propylene oxide and finally with butylene oxide.
However, it is also possible to react a compound of the formula Rl-O-H first with ethylene oxide, then with butylene oxide and then again with ethylene oxide.
Further possible variations are alkoxylating first with propylene oxide, then with ethylene oxide and then again with propylene oxide. There are further conceivable variations for producing the compounds of the formula III, namely addition of alkylene oxides to compounds of the formula R1-O-H in the order ethylene oxide, butylene oxide, propylene oxide or butylene oxide/ethylene oxide/propylene oxide. Preferably, the compounds of the formula III used for producing the essential monomers are the alkoxylation products of monohydric C1-C18-alcohols and of monohydric C3-C1~-alkenols, in particular oleyl alcohol. The alkoxylating agent used is preferably ethylene oxide and/or propylene oxide, preferably used in an amount of from 3 to 100 mol/mol of alcohol. The compounds of the formula III are preferably water-soluble.
The parent carboxylic acids of the amides of thestructure I are for example acrylic acid, methacrylic 2 5~ 3 6 - O.Z. oo50/41782 ~cid, ethacrylic acid, maleic acid, citraconic acid, crotonic acid, fumaric acid, itaconic acid and vinyl-acetic acid. Preferred monomers for preparing the polymers to be used according to the present invention are derived from acrylamide and methacrylamide and have amide groups of the structure I. In what follows, some monomers having amide groups of the structure I are mentioned by way of example:

CH2=CH-CO-NH--CH2--(0--CH2--CH2)7~C13/lsalkyl CH2=CH-CO-NH-CH2--(0--CH2--CH2)3--O--Cl3/l5alky CH2=cH-co-NH-cH2-(o-cH2-cH2)l 1 - O - C 1 3/15alkY
CH2=CH-CO-NH-CH2-(O-CH2-CH2)30-O-cl3/lsalkyl CH2=C(CH3)-CO--NH--CH2--(O--CH2--CH2)7--0--C13/15alkyl CH2=cH-co-NH-cH2-(o-cH2-cH2)26-o-cl6/l3 CH2=c(cH3)-co-NH-cH2-(o-cH2-cH2)3-o-cl3/lsa CH2=C(CH3)--CO--NH--CH2--(0--CH2--CH2)11--O--C13/1salkyl CH2=c(cH3)-co-NH-cH2-(o-cH2-cH2)ll--cl6/l8 CH2=c(CH3)-cO-NH-cH2-(o-cH2-cH2)80-o-cH3 IClH-co-NH-cH2-(o--CH2--CH2)7~C13/lSalkY~
CH-COOH
CH-co-NH-cH2-(o-cH2-cH2)7-o-cl3/l5alkyl CH-co-NH-cH2-(o-cH2--CH2)7---C1 3/15alkYI
CH-co-NH-cH2-(o-cH2-cHz)8-o-(cH-cH~) CH--CO--NH~CH2--(O--CH(CH3)--cH2)6--(o--cH2--cH2) 12{)--CH3 CH-COOH
CO-NH-CH2-(O-CH2-cH2)7-O-c4H9 CH2=C
COOH
CH2=CH-CO-NH-CH2-(O-CH2-CH2)9-O-oleyl CH2=CH-CO-NH-CH2-(0-CH2-CH2)90-O-oleyl CH2-CH~CO~NH~CH2~(O-CH2-CH2)1s-(0-CIH-CH2)3-O-stearyl CH2=CI~CO~NH-CH2-(O-CH2-CH2)25-(O-CH-CH)2--O-palmityl CH2=c-co-NH-cH2-(o-clH--CIH) 3-(0--CH2-CH2)4 2 ~
- 7 - O. Z . 0050/41782 Cg-alkyl CH2=CH--C~I~IH--CH2--(~CH2--CH2) 23{~

CH2=CH-CO-NH--CH2~ CH2--CH2-CH2--CH2) lo{)--Cl 3/1s-alkyl CH 2=CH--C~NH--CH 2--( ~CH 2--CH 2--CH 2--CH 2 ) 1 5~)1 ey I
The abovementioned monomers with amide groups of structure I are polymerized either alone to give homo-polymers or with one another to give copolymers. These polymers are used according to the present invention as detergent additives, as are copolymers of carboxamide groups of the structure I with other ethylenically unsaturated monomers. It is possible to use for example copolymers which contain a) from 10 to 99% by weight of N-(alkyloxypolyalkoxy-methyl)carboxamides of monoethylenically unsaturated C3-C8-carboxylic acids having amide groups of the structure I and b) from 90 to 1% by weight of other monoethylenically unsaturated monomers as copolymerized units. Suit-able monomers of group b) are for example monoethy-lenically unsaturated C3-C8-carboxylic acids, esters thereof with C1-C28-alcohols, esters of monoethylen-ically unsaturated C3-C8-carboxylic acids with reac-tion products of C1-C28-alcohols and ethylene oxide, propylene oxide and/or butylene oxide i~ a molar ratio of from 1:1 to 1:100, amides, N-C1-C18-alkyl-oxymethylamides and nitriles of monoethylenically unsaturated C3-C8-carboxylic acids, vinyl esters of saturated carboxylic acids of from 1 to 20 carbon atoms, C1-C28-alkyl vinyl ethers, styrene or mixtures thereof.
Suitable monoethylenically unsaturated C3-C8-car-boxylic acids are for example acrylic acid, methacrylic acid, vinylacetic acid, 2-ethylacrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid. Preference i5 given to using acrylic acid, methacrylic acid and maleic acid.

- 8 - O.Z. 0050/41782 Suitable esters of the abovementioned carboxylic acids with C1-C28-alcohols are for example methyl acry-late, methyl methacrylate, ethyl acrylate, ethyl meth-acrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, the corresponding butyl esters of methacrylic acid, 2-ethyl-hexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, isobutyl acrylate, isobutyl methacrylate, palmityl acrylate, palmityl methacrylate, stearyl acry-late, stearyl methacrylate, dimethyl maleate, diethyl maleate, di-n-propyl maleate, diisopropyl maleate, di-n-butyl maleate, maleic esters of cyclohexanol, dodecyl alcohol and octadecyl alcohol, acid esters of maleic acid, such as methyl hydrogen maleate, cyclohexyl h~,rdrogen maleate, 2-ethylhexyl hydrogen maleate, and octadecyl hydrogen maleate, the corresponding neutral and acid esters of fumaric acid with saturated monohydric C1-C28-alcohols, dimethyl itaconate, diethyl itaconate, di-n-pxopyl itaconate and diisopropyl itaconate.
It is also possible to use polymers which con-tain, as copolymerized units of comonomers of group b), esters of monoethylenically unsaturated C3-C8-carboxylic acids and polyhydric alcohols, eg. hydroxylethyl [sic~
acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl meth~crylate, hydroxybutyl acrylate, hydroxybutyl m0thacrylate and the esters of acrylic, methacrylic and maleic acids with 1,6-hexane-diol.
Suitable esters of monoethylenically unsaturated C3-C~-carboxylic acids with reaction productA of alcohols and alkylene oxides are for example the esters of acrylic acid and methacrylic acid with ethoxylated C1-C28-alcohols formed by addition of from 1 to lO0 mol of ethylene oxide to 1 mol of a monohydric or polyhydric alcohol. The alcohols may also be ethoxylated with mixtures of alky-lene ox.ides, for example mixtures of ethylene oxide, - 9 - O.z. 0050/41782 propylene oxide and/or butylene oxide, in which case random addition products of the alkylene oxides with the alcohols are obtained. Further variations are possible by reacting the alcohols first with, for example, ethylene oxide and then with propylene oxide and/or butylene oxide, or by varying the order of addition of the alky-lene oxides to the alcohols. Such a step-by-step addition of alkylene oxides to alcohols produces alkoxylated alcohols which contain the added alkylene oxides in the form of copolymerized blocks. Of the addition products of alkylene oxides with alcohols it is possible to use not only the esters of acrylic acid or methacrylic acid but also the esters of other abovementioned carboxylic acids, for example the maleic, fumaric and itaconic esters of the addit.ion products. Of the dibasic carboxylic acids, it is possible to use not only the monoesters but also the diesters.
Further suitable monomers of group b) are Cl-C2a-alkyl vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether. Another possible monomer of group b) is styrene.
Of the amides and nitriles of monoethylenically unsaturated C3-C8-carboxylic acids, in particular acryla-mide, methacrylamide, acrylonitrile and methacrylonitrile come into consideration.
N-Alkyloxymethylcarboxamides having Cl-Cl8-alkyl moieties are used as starting materials for preparing the monomers a) by reaction with alkoxylated alcohols, and also as monomers of group b). Examples of such starting materials are: N-methoxymethylacrylamide, N-methoxy-methylmethacrylamide,N-ethoxymethylacrylamide,N-ethoxy-methylmethacrylamide, N-propoxymethylacrylamide, N-prop-oxymethylmethacrylamide, N-isopropoxymethylacrylamide, N-isopropoxymethylmethacrylamide, N-butoxymethyl-2~
- 10 - O.Z. 0050/41782 acrylamide, N-btuoxymethylmethacrylamide [sic], N-isobutoxymethylacrylamide, N-isobutoxymethylmeth-acrylamide, N-tert-butoxymethylacrylamide, N-tert-butoxymethylmethacrylamide, and higher homologs such as N - d e c y 1 o x y m e t h y l a c r y 1 a m i d e , N-decyloxymethylmethacrylamide, N-octadecyl-oxymethylacrylamide, N-octadecyloxymethylmethacrylamide, N-isotridecanoxymethylacrylamide, N-isotridecanoxy-methylmethacrylamide but also with C3-Cl8-alkenyl moieties, for example N-propenyloxymethylacrylamide, N-propenyloxymethylmethacrylamide, N-butenyloxymethyl-acrylamide, N-butenyloxymethylmethacrylamide, N-oleyl-oxymethylacrylamide, N-oleyloxymethylmethacrylamide and mixtures thereof.
Of the N-alkoxymethylcarboxamides, preference is given to using N-butoxymethylacrylamide, N-butoxymethyl-methacrylamide, N-isobutoxymethylacrylamide and N-iso-butoxymethylmethacrylamide. Suitable vinyl esters of saturated carboxylic acids of from 1 to 20 carbon atoms are for example vinyl formate, vinyl acetate~ vinyl propionate, vinyl butyrate, vinyl pivalate and vinyl stearate.
Further suitable monomers of group b) are:
N-vinylpyrrolidone,N-vinylcaprolactam,N-vinylformamide, N-vinylacetamide and sulfo-containing monomers, such as acrylamidopropanesulfonic acid, allylsulfonic acid, vinylsulfonic acid and the alkali metal and ammonium salts thereof.
The monomers of group b) can be used in the preparation of polymers either alone or in the form of mixtures. The polymers may contain for example acrylic acid and maleic acid or methacrylic acid and maleic acid as copolymerized monomers of group b). Other preferred monomer combinations are for example acrylic acid and vinyl acetate, acrylic acid and vinyl propionate, acrylic acid and ethyl acrylate, acrylic acid and ethyl methacry~
late, acrylic acid ancl methyl acrylate, acrylic acid and ~ O.Z. 0050/41782 methyl methacrylate and also acrylic acid and N-butoxy-methylacrylamide, acrylic acid and N-butoxymethyl-methacrylamide, acrylic acid and N-isobutoxymethyl-acrylamide, acrylic acid and N-isobutoxymethylmeth-acrylamide and also methacrylic acid and vinylpropionate. ~he monomers of group b) are preferably involved in the formation of the copolymers in a prspor-tion of from 1 to 90~ by weight.
The polymers may contain as copolymerized units of group c) monomers having at least two ethylenically unsaturated double bonds. Such chain extender compounds are for example diacrylates or dimethacrylates of at least dihydric saturated alcohols, eg. ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, neo-pentylglycol diacrylate, neopentylglycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol methacrylate ~sic]. Suitable chain extenders also include acrylic and methacrylic esters of alcohols having more than two hydroxyl groups, eg. trimethylolpropane triacry-late and trimethylolpropane trimethacrylate. A further class of chain extenders are the acrylates and methacry-lates of polyethylene glycols or polypropylene glycols ofmolecular weights which are preferably in both cases within the range from 400 to 2,000. Beside~ the diacry-lates and dimethacrylates of the homopolymers of ethylene oxide or propylene ox~de, it is also possible to use block copolymers of ethylene oxide and propylene oxide or random copolymers of ethylene oxide and propylene oxide, which are each esterified in the ~,~-position with acrylic acid, methacrylic acid, maleic acid or itaconic acid. Chain extenders of this kind are for example esters of glycols with maleic acid in a molar ratio of 1:2, diethylene glycol diacrylate, diethylene glycol dimeth-acrylate, triethylene glycol dimethacrylate, tetraethy-2 ~
- 12 - O.Z. 0050/41782 lene glycol diacrylate and/or tetraethylene glycol dimethacrylate and also the diacrylates or dimethacrylate [sic] of polyethylene glycol of molecular weight 1,500.
Suitable monomers of group c) also include vinyl esters of ethylenically unsaturated C3-C8-carboxylic acids, for example vinyl acrylate, vinyl methacrylate or vinyl itaconate. It i5 also possible to use the vinyl esters of at least dibasic saturated carboxylic acids and also the di- and polyvinyl ethers of at least dihydric alcohols, for example divinyl adipate, butanediol divinyl ether and trimethylolpropane trivinyl ether. Further monomers of group c) are for example allyl esters of ethylenically unsaturated carboxylic acids, eg. allyl acrylate and allyl ether, triallyl sucrose and pentaallyl sucrose.
Similarly, methylenebisacrylamide, methylenebis-methacrylamide, N-divinylethyleneurea, divinylbenzene, divinyldioxane, tetraallylsilane and tetravinylsilane are suitable for use as monomers of group c). If the monomers of group c) are used for the preparation of the polymers, they will be present in the polymers in polymerized form in amounts of from 0.01 to 20, preferably from 0.05 to 10~ by weight. The monomers of group c) can be used either alone or mixed with one another.
The polymers to be used according to the present invention are obtainable by polymerizing the monomers a) alone or mixed with at least one monomer of group b) and/or group c). They can be prepared by any customary polymerization process, for example by bulk, solution, precipitation or suspension polymerization. Preferably, the copolymers are produced by solution polymerization.
In any event, the polymerization is carried out using free radical initiators. The polymeriza~ion temperatures range from 20 to 200, preferably from 30 ko 150 C.
The mono- and dicarboxylic acids of the monomers of group b~ can be used in ~he copolymerization not only in the form of free carboxylic acids but also in a partially or even completely neutralized form. The degree 2 ~
- 13 - O.Z. 0050/41782 of neutrali~ation - in particular if dicarboxylic acids are used as monomers of group b) - can have an appreciable influence on the course of the polymeriza-tion, for example conversion, rate, molecular weight and residual monomer content of the copolymer. The carboxylic acids may be neutralized by inorganic or organic bases, for example sodium hydroxide solution, potassium hydroxide solution, ammonia, amines, such as dimethyl-amine, triethanolamine, triethylamine, trimethylamine, tributylamine, ethanolamine or diethanolamine. It is also possible to use mixtures of different bases, for example mixtures of sodium hydroxide solution and trie~hanol-amine. If the copolymerization is carried out in aqueous solutions, then the monomers of group b) with acid groups are preferably used in the neutralized form. The pH Gf the aqueous monomer solution is preferably above 6.5, for example within the range from 7 to 11 or even higher. In water-free media it is also possible to use the non-neutralized carboxylic acid.
Suitable initiators include ~11 free radical donors known for this purpose. These initiators may be soluble or else insoluble in water. Water-soluble initia-tors are for example inorganic peroxides, such as potas-sium peroxodisul~ate, sodium peroxodisulfate, ammonium peroxodisulfate and hydrogen peroxide. It i5 also pos~
sible to use organic peroxides, hydroperoxides, peracids, ketone perox:ides, perketals and peresters, eg. methyl ethyl ketone hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-(di-tert-butylperoxy)cyclo-hexane, di-(tert-butyl) peroxide, tert-butyl peroxypiva-late, ethylhexyl peroctoate, tert-butyl monoperoxy-maleate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide and mixtures thereof. It is also possible to use redox systems which in addition to a peroxy compound contain a reducing component. Suitable reducing components are ~or example cerium(III) and iron(II) salts, sodium sulfite, 2 ~

- 14 - o.z. 0050/41782 sodium hydrogensulfite, sodium dithionite, ascorbic acid and sodium formaldehydesulfoxylate. Preferred initiators have a half-life of less than three hours at the particular polymerization temperature. If the polymeriza-tion is started at a low temperature and completed at a high temperature, it is advantageous to use at least two initiators which decompose at different temperatures, namely first an initiator which decomposes at a low temperature for the start of the polymerization and then an initiator which decomposes at a higher temperature for the main polymerization. By adding heavy metal salts, for example copper, cobalt, manganese, iron, nickel and chromium salts, to peroxidic catalysts it is possible to lower the decomposition temperatures of the latter.
Suitable initiators also include azo compounds, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopro-pane) dihydrochloride, 2,2'-azobis(2-methylpropionami-dine~ dihydrochloride, 2,2'-azobis(2,4-dimethylvalero-nitrile) and dimethyl 2,2~-azobisisobutyrate. Particular preference is given to hydrogen peroxide, potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxo-disulfate, tert-butyl perpivalate, 2,2'-azobis(2,4-di-methylvaleronitrile) and di-tert-butyl peroxide for use as polymerization initiator. Based on the monomers to be polymerized, the initiator or initiator mixture is custo-marily used in an amount of from 0.5 to 10, preferably from 1 to 8, % by weight. The amount of initiator has -as will be known - an appreciable influence on the molecular weight of the homo- or copolymer product.
As previously mentioned, the polymerization is preferably carried out in the presence of a diluent. It may be a solvent for the monomers and the polymers or merely a solvent for the monomers. Suitable solvents for a solvent polymerization are for example aromatic hydro-carbons, such as toluene, xylene, cumene and tetralin, aliphatic hydrocarbons, such as hexane, heptane, octane, cyclohexane and isooctane, and preferably ethers, such as 2 ~ L

- lS - o. z . 0050/41782 diethyl ether, dibutyl ether, diisobutyl ether, methyl tert-butyl ether, cyclic ethers, such as tetrahydrofuran and dioxane, monoalkyl or dialkyl ethers of mono- or polyethylene glycols, eg. ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, monoalkyl ethers of mono- or polyethylene glycol acetates, such as methyl-glycol acetate, butylglycol acetate, methyldiethylene - glycol acetate, butyldiethylene glycol acetate, and addition products of alkylene oxides of from 2 to 4 carbon atoms with alcohols or alkylphenols. The molecular weights of these addition products can be up to 8,000, preferably up to 6,000. If at least 2 different alkylene oxides are used for preparing the addition products, the alkylene oxide units can be present in the reaction products in random distribution or in the form of blocks.
Such reaction products are constituents of liquid deter-gents. Since the polymers are used in detergents, they are advantageously prepared in the above-described addition products as solvents and the polymer solution obtained can be used directly for preparing the detergent formulation.
Preferred solvents for the polymerization are for example reaction products of monohydric aliphatic Cl-C23-~5 alcohols or Cl-Cl8-alkylphenols with ethylene oxide, propylene oxide and/or butylene oxide, for example the addition products of from 3 to 11 mol of ethylene oxide with one mol of a Cl3/Cl5-alcohol, addition products of from 5 to 15 mol of etnylene oxide with 1 mol of nonyl-phenol, addition products of from 7 to 11 mol of ethyleneoxide and from 3 to 5 mol of propylene oxide with 1 mol of oleyl alcohol, and addition products of from 5 to 15 mol of ethylene oxide with 1 mol of stearyl alcohol or tallow fat alcohol. It is also possible to use the addition products of ethylene oxide, propylene oxide and butylene oxide with polyhydric alcohols eg. glycol, diethylene glycol, tetraethylene glycol, propylene 2~3~
_ 16 - O.Z. 0050/41782 glycol, dipropylene glycol, block copolymers of ethylene oxide and propylene oxide, glycerol and oligoglycerols.
Among this group of compounds, diethylene glycol is particularly preferred.
Further suitable solvents are C1-C6-alcohols, such as methanol, ethanol, isopropanol, n-propanol, butanols, n-hexanol and cyclohexanoll ketones, eg. acetone, ethyl methyl ketone and cyclohexanone, esters, eg. ethyl acetate, and water and mixtures of water with water-soluble organic solvents. If an inert solvent is used in the polymerization, the concentrations of the monomers therein are from 10 to 90, preferably from 15 to 70, ~ by weight.
The polymerization of the monomers of groups a) to c~ may additionally be carried out in the prese~ce of regulators. Suitable regulators are for example mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butylmercaptan and dodecylmercaptan. Suitable regulators also include allyl compounds, such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydroxyl-ammonium sulfate and butenols. Regulators are used in particular when relatively large amounts of monomers of group c) are used in the polymerization. Owing to the use of regulators, the products in such cases are polymers which are soluble or readily dispersible in water. If the polymerization is carried out in the presence of regulators, they are used in an amount of from 0.05 to 20% by weight, based on the monomers to be polymerized.
The polymerization is carried out in customary apparatus equipped with mixing elements. It is possible to use for example stirrer-equipped pistons, kettles, autoclaves and cylindrical reactors. The polymerization may also be carried out in kettles, cascades or intercon-nected polymerization apparatus. The polymerization may - 17 - O.Z. 0050/~1782 be carried out batchwise or continuously. Suitable polymerization apparatus also includes kneaders. If water-soluble monomers are used in the polymerization, - the polymerization may also be carried out by the method of reverse suspension polymerization or by the method of water-in-oil emulsion polymerization. Preferably, however, the polymerization is carried out as a solution polymerization. For special purposes the preparation of polymers by the method of precipitation polymerization may be of interest. The polymerization may be initiated not only by the catalytic action of compounds which decompose into free radicals under the polymerization conditions but also by the action of high-energy radia-tion, for example by W radiation or by the action of ~-, ~- or ~-rays. At temperatures above the boiling point of the particular solvent or solvent mixture used, the polymerization is customarily carried out in pressure-tight apparatus. Preferably, the polymerization takes place in the absence of oxygen, in an inert gas atmo-sphere, for example nitrogen, argon, helium or carbondioxide, under atmospheric pressure.
In the case of relatively small polymerization batches, where the heat of polymerization can be removed sufficiently rapidly, it is possible to introduce the monomers to be polymerized together with at least one polymerization initiator and to polymerize the mixture by heating to the particular polymerization temperature required. It is more advantageous, however, to charge the polymerization apparatus initially with only some of the monomers and initiator and to add the remaining monomers and initiator continuously or batchwise at a rate com-mensurate with the rate of polymerizati.on. The monomers of components a) and b) may be introduced into the polymerization reactor either in the form of a solution or else without a diluent. In a particularly preferred embodiment, the monomers of groups a) and b) are mixed and metered in the form of a solution in an inert solvent 2 ~
- 18 - O.Z. 0050/41782 continuously or batchwise into a polymerization reactor.
However, the monomers may also be introduced into the polymerization reactor separately from one another without a solvent or in the form of a solution. Depending on the choice of monomers and polymerization conditions, the products obtained are homopolymers or copolymers having K values of from 8 to 2~0, preferably from 10 to 100 .
If the polymerization is carried out in an organic solvent, it is advantageous for the copolymer to be first neutralized and only then converted into an aqueous solution or dispersion which is then used as a detergent additive. If it is necessary to separate off the organic solvent, this may be done for example by lS distillation.
The above-described polymers, containing as an essential building block N(alkyloxypolyalkoxymethyl)car-boxamides [sic] of monoethylenically unsaturated C3-Ca-carboxylic acids having amide groups of the structure I, are used as detergent additives to increase the primary and secondary detergency of detergent formu-lations. The detergents contain as essential ingredients not only the above-described polymers, in an amount of from 0.1 to ~0% by weight, but also at least one anionic or nonionic surfactant or a mixture thereof. The deter-gents can be present in powder or liquid form. The copolymers to be used according to the present invention are suitable in particular for preparing liquid detergent formulations.
Suitable anionic surfactants are for example sodium alkylbenzenesulfonates, fatty alcohol sulfates and fatty alcohol polyglycol ether sulfates.
Individual compounds of this type are for example C8-Cl2-alkylbenzenesulfonates, Cl2-Cl~-alkanesulfonates, C12-C16-alkyl sulfates, C12-C16-alkylsulfosuccinates and sulfated ethoxylated C12-C16-alkanols. Other suitable anionic surfactants are sulfated fatty acid alkanol-2 ~

- 19 - O. Z . 0050/417g2 amides, fatty acid monoglycerides or reaction products of from 1 to 4 mol of ethylene oxide with primary or secondary fatty alcohols or alkylphenols. Further suitable anionic surfactants are fatty acid esters or amides of hydroxy- or amino-carboxylic or -sulfonic acids, for example the fatty acid sarcosides, glycolates, lactates, taurides or isothionates [sic]. The anionic surfactants can be present in the form of the sodium, potassium or ammonium salts or the soluble salts of organic bases, such as mono-, di- or triethanolamine or other substituted amines. The anionic surfactants also include the ordinary soaps, ie. the alkali metal salts of natural fatty acids.
Suitable nonionic surfactants are for example addition products of from 3 to 40, preferably 4 to 20, mol of ethylene oxide with 1 mol of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide. Of particular importance are the addition products of from 5 to 16 mol of ethylene oxide with coconut or tallow fat alcohols, with oleyl alcohol or with synthetic alcohols of from 8 to 18, preferably from 12 to 18, carbon atoms, and also with mono- or dialkylphenols having from 6 to 14 carbon atoms in the alkyl moietiesO In addition to these water-soluble nonionics, however, it is also possible to use water~
insoluble or incompletely water~soluble polyglycol ethers having from 1 to 4 ethylene glycol ether moieties in the molecule, in particular together with water-soluble nonionics or anionics. Other usable nonionic surfactants are the water-soluble addition products of ethylene oxide with polypropylene glycol ether, alkylenediaminopoly-propylene glycol and alkylpolypropylene glycols having from 1 to 10 carbon atoms in the alkyl chain that contain from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups and in which the polypropylene glycol ether chain acts as hydrophobe.
It is also possible to use nonionic surfactants ~$$~
- 20 - o.z. 0050/41782 of the type of the amine oxides or sulfoxides.
The foaming power of the surfactants can be boosted or reduced by combining suitable surfactant types. A reduction can likewise be achieved by adding non-surfactant-type organic substances.
The liquid, aqueous detergents contain from 10 to 50% by weight of surfactant. Said surfactant may be an anionic surfactant or a nonionic surfactant or it may be a mixture of the two. If the latter, the anionic surfac-tant content of liquid detergent should be from 10 to 30%by weight and the nonionic surfactant content of the liquid detergent should be from 5 to 20% by weight, based on the detergent formulation as a whole.
Liquid detergents contain the copolymers to be used according to the present invention as essential components in an amount of from 0.1 to 20, preferably from 1 to 10, % by weight and optionally water in amounts of from 10 to 60, preferably from 20 to 50, % by weight.
Liquid detergents may also contain further, modifying substances. They include for example alcohols, such as ethanol, n-propanol and isopropanol. These substances, if used at all, are used in an amount of from 3 to 8% by weight, based on the detergent formulation as a whole. Liquid detergents may also contain hydrotropes.
These are compounds such as 1,2-propanediol, cumene-sulfonate and toluenesulfonate. If such compounds are used for modifying liquid detergents, their amount is from 2 to 5% by weight, based on the total weight of the liquid detergent. In many cases it will be advantageous to add complexing agents as modifiers. Complexing agents are for example ethylenediaminetetraacetic acid, nitrilo-triacetate and isoserinediace~ic acid and also phospho-nates, such as aminotrismethylenephosphonic acid, hydroxyethanediphosphonic acid, ethylenediaminetetra-methylenephosphonic acid and salts thereof. The complex-ing agents are used in amounts of from 0 to 10% by weight, based on the liquid detergent. The liquid deter-- 21 - O.z. OQ50/41782 gents may also contain citrates, di- or triethanolamine, opacifiers, optical brighteners, enzymes, perfume oils and dyes. These substances, if present at all in a liquid detergent as modifiers, are present together in amounts of up to 5~ by weight. The liquid detergents are preferably phosphate-free. However, they may also contain phosphates, for example pentasodium triphosphate and/or tetrapotassium pyrophosphate. If phosphates are used, the phosphate content of the total formulation of the liquid detergent is from 10 to 25% by weight, calculated as pentasodium triphosphate.
The above-described liquid detergents have the advantage over pulverulent detergents of being easily meterable and possess very good grease and oil dissolving power in relation to grease-stained laundry at lower wash temperatuxes. Liquid detergents contain high proportions of active detergent substances which bring about the removal of soil from the textile fabric even at wash temperature of 40 to 60C. Hitherto the dispersing properties of polymers could not be utilized in aqueous liquid detergents since, as a consequence of high elec-trolyte concentrations in the deter~ents, it was impos-sible to obtain stable solutions with the polymers. The homopolymers and copolymers to be used according to the present invention, then, make it possible to prepare stable aqueous solutions of liquid detergents and to distinctly improve the washing characteristics of liquid detergents. ~he effectiveness in liquid detergents of the homopolymers and copolymers to be used according to the present i~vention is demon~trated in the Examples by reference to the pximary and secondary detergency of these detergents. Primary detergency is the process of actual soil removal from the textile material. The degree of soil removal is determined as the difference in the whiteness between the washed and the unwashed textile material. The textile test material used is a cotton, cotton/polyester or polyester fabric with standard 2 ~ i$ ~
- 22 - o.z. 0050/41782 soiling. After every wash, the whiteness of the fabric is determined in % reflectance in an Elrepho photometer from Zeiss.
Secondary detergency is the detersive effect relating to the redeposition of detached soil on the fabric in the wash liquor. Secondary detergency only becomes relevant after several washes, for example 3, 5, 10 or even 20 washes, which show an increase in grayness of the fabric due to redeposition of soil on the fabric from the wash liquor. To determine the graying, standard soil cloths are repeatedly washed together with white test fabric, the soil cloth being renewed after every wash. The soil detaching from the soil cloth and deposi-ting on the white test fabric during the wash causes a drop in whitenes~, which is measured. The homopolymers and copolymers or water-soluble salts thereof to be used according to the present invention in detergents can also be used for formulating pulverulent detergents (washing powders).
The composition of washing powder formulations can vary widely. The same is true of detergent formula-tions used as cleaners. Any kind of detergent formulation customarily contains surfactants with or without builders. This is true not only of liquid but also of pulverulent detergents. Examples of the composition of detergent formulations customary in Europe, the USA and Japan may be found for e~ample in Chemical and Engineer-ing News, 67 ~1989), 35, in table form and Ullmanns Encyklopadie der technischen Chemie, Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160.
In the Examples the percentages are by weight.
The ~ values were determined by the method of H.~ikentscher, Zellulosechemie, 13 (1932) 58-64, 71-74.
The K values of the water-soluble polymers were deter-mined in aqueous solution at 25C at pH 7.5 and a polymer concentration of 1% by weight.
The K values of the water-dispersible polymers - 23 - o.z. 0050/41782 were determined as 1% streng~h solutions in the non-neutralized form in ~etrahydrofuran (T~F) at 25C. The K
values thus determined are in all cases within the range from 8 to 200, preferably from 10 to 100.
EXAMPLES
Preparation of polymers The following compounds were used as monomers of group a):
Acrylamide derivative 1:
CH2=cH-co-NH-cH:~-(O-cH2-cH2)7-O-cl3~l5-alkyl Acrylamide derivative 2:
CH2=cH-co-~H-cH2-(O-cH2-cH~)3~~Cl3~ls~alkY
Acrylamide derivative 3:
CH2=CH-CO-NH-CH2-(O-CH2-CH2)ll-O-Cl3~l5-alkyl Acrylamide derivative 4:
CH2=cH-co-NH-cH2-(-CH2-cH2)?.5-0-c16/l8 Polymer 1 A 500 ml round-bottomed flask equipped with a stirrer, a reflux condenser, a nitrogen inlet and feed means is charged under nitrogen with 125 g of tetrahydro-furan, which are heated to the boil under reflux. This initial charge is then mixed from 3 feed vessels simul-taneously with a solution of 37.5 g of acrylic acid in 35 g of tetrahydrofuran and a solution of 37.5 g of acrylamide derivative 1 in 35 g of tetrahydrofuran, each added over 1 hour, and a solution of 1.5 g of 2,2~-azo-bis(2,4-dimethylvaleronitrile) in 20 g of tetrahydro-furan, added over 2 hours. After the initiator has all been added, the reaction mixture is refluxed at the boil for a further 2 hours, cooled down to 20C and neutral-ized with a mixture of 124 g of triethanolamine and 50 g of tetrahydrofuran. The waxy contents of the flask are admixed with 300 g of water, and the solution obtained is freed of tetrahydrofuran by distillation. This leaves a slightly yellowish, clear, aqueous, viscous solution having a solids content of 27% and a K value of 32 (measured in aqueous solution).

2 ~
- 24 ~ O.Z. 0050/41782 Polymer 2 The apparatus described in Example 1 is charqed with 200 g of diethylene glycol dLmethyl ether, which are heated to 140C under nitrogen and then admixed at that temperature over 2 hours with a mixture of 70 g of acrylic acid and 30 g of acrylamide derivative 1 and at the same time over 2.5 hours with a solution of 4 g of di-tert-butyl peroxide in 50 g of diethylene glycol dimethyl ether, in each case dropwise. Then the reaction mixture is cooled down to 20C and neutralized with 78 g of 50% strength aqueous sodium hydroxide solution. The reaction mixture is then concentrated in an aspirator vacuum and the copolymer is precipitated with 1 1 of cyclohexane. The polymer is filtered off and dried at 100C under reduced pressure. Water is added to prepare a 35% strength aqueous solution having a K value of 18 (measured in aqueous solution).
Polymer 3 A 2 1 capacity polymerization apparatus equipped with a stirrer, a nitrogen inlet, a nitrogen outlet and feed vessels is charged with 500 g of isopropanol, which are heated to the boil under reflux. As the contents begin to boil they are admixed from 3 feed vessels over 3 hours with 150 g of acrylic acid on the one hand and 150 g of acrylamide derivative 1 in 125 g of isopropanol on the other [lacuna] over 4 hours with 6 g of 2,2'-azo-bis(2,4-dLmethylvaleronitrile) in 75 g of isopropanol.
After the initiator has all been added, the reaction mixture is refluxed for a further hour, cooled down and neutralized with 83 g of 50% strength aqueous sodium hydroxide solution. Isopropanol is then distilled off and replaced by water to produce a clear solution having a solids content of 46%. The K value of the copolymer is 20.5 (measured in aqueous solution).
Polymer 4 An aqueous solution of 135 g of acrylic acid in 150 g of water is neutralized with 227 g of 50% strength 2 ~ 3 ~
- 25 - o.z. 0050/41782 aqueous potassium hydroxide solution and admixed with a solution of 67 g of acrylamide derivative 1 in 200 g of isopropanol. The resulting clear solution and separately therefrom a solution of 2 g of mercaptopropionic acid in 20 g of water and 20 g of isopropanol are added over 1 hour continuously to the polymerization apparatus described in connection with the preparation of polymer 3, and polymerized at a bath temperature of 90C by adding 6.7 ~ of 30% strength aqueous hydrogen peroxide 10 dissolved in 30 g of water and 30 g of isopropanol as polymerization initiator over 2 hours. After the hydrogen peroxide has been added, the reaction mixture is refluxed for a further 2 hours and the excess isopropanol is distilled off. This leaves a cloudy solution having a 15 solids content of 38%. The K value of the polymer is 26 (measured in aqueous solution). The 38~ strength aqueous solution becomes clear and colorless on being diluted to a solids content of about 15% by weight.
Polymers 5 to 12 The apparatus described for the preparation of polymer 3 is charged with 100 g of tetrahydrofuran, which are heated to the boil under reflux. ~s the contents begin to boil they are admixed in the course o~ 2 hours with a solution of 140 g of acrylamide derivative 1 and 25 60 g of acrylic acid in 100 g of tetrahydrofuran and in the course of 2.5 hours with a solution of 8 g of 75%
strength tert-butyl perpivalate in 50 g of tetrahydro-furan. Aftex the initiator has all been added, the reaction mixture is heated at the boil for a further 30 hour, cooled down and then neutralized with 67 g of 50%
strength aqueous sodium hydroxide solution and 400 g of water. The tetrahydrofuran is then distilled off and the solids content of the aqueous solution is then adjusted to 15% with water. The 15% strength aqueous solution has 35 a viscosity of 1,062 mPas at 20C. The K value is 25.6 (measured in aqueous solution).
The aforedescribed method is also used to prepare ~ ~3 ~
- 26 - O~Z. 0050/41782 polymers 6 to 12 from the starting materials shown in Table 1.

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- 28 - O.Z. 0050/41782 Polymer 13 The apparatus described in connection with the preparation of polymer 1 is charged under nitroqen with 60 g of tetrahydrofuran, which are heated to the boil under reflux. At the onset of boiling a solution of 30 g of acrylamide derivative 3, and 70 g of hydroxyethyl acrylate in 50 g of tetrahydrofuran are each added dropwise over 2 hours and a solution of 2 g of 75%
strength tert-butyl perpivalate in 50 g of tetra-hydrofuran is added dropwise over 3 hours, and after theperoxide has all been added the reaction mixture is refluxed for a further 2 hours. It is then concentrated to dryness in the vacuum of an aspirator. The residue comprises 106 g of a colorless resin having a K value of 14 (determined on aqueous polymer solutions).
Polymer 14 The apparatus described in connection with the preparation of polymer 3 is charged with 200 g of tetra-hydrofuran, which are heated to the boil under reflux.
The boiling solution is admixed with a solution of 70 g of acrylamide derivative 1 and with a solution of 25 g of vinyl acetate and 5 g of acrylic acid in 100 g of tetra hydrofuran, each added dropwise over 2 hours, and with a solution of 4 g of 75% strength tert-hutyl perpivalate in 50 g of tetrahydrofuran, added dropwise ovex 3 hours.
After the peroxide has all been added, the reaction mixture is heated at the boil for a further 3 hours and then cooled. 5.5 g of 50% strength aqueous sodium hydrGxide solution and 350 g of water are added, and the tetrahydrofuran is distilled off. This leaves a homo-geneous solution having a solids content of 30% and a viscosity of 1,229 mPas. The K value of the polymer in the non-neutralized form is 12.1 (determined on solutions of the polymer in THF).
Polymer 15 The preparation of polymer 14 is repeated, except that acrylamide derivative 1 is replaced by acrylamide - 29 ~ O.Z. 0050/41782 derivative 3. A 30% strength solu~ion is obtained having a viscosity of 9,788 mPas. The K value of the polymer in the non-neutralized form is 16.8 (determined on solutions of the polymer in THF).
Polymer 16 The preparation of polymer 14 i5 repeated, except that 50 g of acrylamide derivative 3, 40 g of vinyl acetate and 10 g of acrylic acid are polymerized in 100 g of tetrahydrofuran using 4 g of 75~ strength tert-butyl perpivalate in 50 g of tetrahydrofuran. After the poly-merization 11 g of 50% strength a~ueous sodium hydroxide solution in 200 g of water are added. Distillation and dilution of the mixture with water gives a very cloudy 30% strength polymer solution having a viscosity of 12,833 mPa The K value of the polymer in the non-neutralized form was 20.3 (determined on solutions of the polymer in THE').
Polymer 17 The apparatus used for the preparation of polymer 1 is charged with 30 g of tetrahydrofuran, which are heated to the boil. 50 g of acrylamide derivative 2 dissolved in 50 g of tetrahydrofuran are then added in the course of 2 hours and a solution of 1 g of 75%
strength tert-butyl perpivalate dissolved in 50 g of tetrahydrofuran is added over 3 hours. After the initia-tor has all been added, the reaction mixture is refluxed at the boil for a further 2 hours and then evaporated under a reduced pressure of 10 mbar, and the residue is dried to constant weight. This leaves 51 g of a colorless resin having a K value of 18.5 (determined in 1~ strength solution in tetrahydrofuran). The polymer is only par-tially soluble in water, but it is readily soluble in tetrahydrofuran, isopropanol and ethyl acetate.
Polymer 18 The preparation of polymer 14 is repeated, except that S0 g of acrylamide derivative 3, 40 g of N-(isobutoxymethyl)acrylamide and 10 g of acrylic acid in 2 ~
- 30 - o.z. 0050/41782 100 g of tetrahydrofuran are polymerized with 4 g of 75%
strength tert-butyl perpivalate in 50 g of tetrahydro-furan and the polymerization mixture is then neutralized with 11 g of 50% sodium hydroxide solution and diluted with 200 g of water. The tetrahydrofuran is distilled off to leave a slightly cloudy solution having a solids content of 38% and a viscosity of 3,420 mPas. The K value was 19.1 (determined on solutions of the polymer in THF).
Polymer 19 The preparation of polymer 14 is repeated, except that 50 g of acrylamide derivative 3, 40 g of N-(iso-butoxymethyl)acrylamide and 10 g of acrylic acid in 100 g of tetrahydrofuran are polymerized using 4 g of 75~
strength tert-butyl perpivalate in 50 g of tetrahydro-furan and the polymerization mixture is neutralized with 11 g of 50% strength sodium hydroxide solution. 200 g of water are then added to leave, after distillation, a solution which when warm is very cloudy and when cold only slightly cloudy and has a solids content of 40% and a viscosity of 2,432 mPas. The K value is 18.2 (deter-mined on aqueous polymer solutions).
Polymer 20 The preparation of polymer 14 is repeated, except that 50 g of acrylamide derivative 1 and 50 g of N-(iso-butoxymethyl)acrylamide in 100 g of tetrahydrofuran are polymerized using 4 g of 75% strength tert-butyl perpiva-late in 50 g of tetrahydrofuran. After th0 polymerization has ended, 200 g of water are added, the tetrahydrofuran i8 distilled off and 150 g of isopropanol are added. This gives a cloudy suspension having a solids content of 26.7~ and a viscosit~ of 18 mPas. The K value is 15.1 (measured on 1% strength polymer solution in THF).
Polymer 21 A 2 1 reaction vessel equipped with an efficient mechanical stirrer, a nitrogen conn0ction and metering vessels is charged with 130 g of a reaction product of 7 mol of ethylene oxide and 1 mol of a C13/ls oxo process - 31 - O.Z. 0050/41782 alcohol under nitrogen and the contents are heated to 70aC. 3 metering vessels are employed to add in the course of 2 hours 60 g of acrylic acid, a mixture of 15 g of acrylamide derivative 1 and 60 g of a reaction product of 7 mol of ethylene oxide and 1 mol of a C13/15 oxo process alcohol and a solution of 2 g of 75~ strength tert-butyl perpivalate in 20 g of polypropylene glycol (molecular weight 600). A further 0.5 g of 75% strength tert-butyl perpivalate are then added in one portion, and the mixture is stirred at 70C for a further hour. After it has been cooled down to 20C, it is neutralized with 124 g of triethanolamine and 350 g of water. The solution obtained contains 26.3% of neutralized copolymer whose K
value is 60.2 (measured in 1~ strength in water)~
Polymers 22-27 The method given for the preparation of polymer 21 is also used to prepare polymers 22-27 using the starting materials listed in Table 2.

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_ 34 _ o.z. 0050/41782 Polymer 28 A mechanically stirred 250 ml round-bottomed flask equipped with a reflux condenser and metering means is charged with 60 g of tetrahydrofuran, which are heated to the boil. This initial charge is admixed in the course of 30 minutes with a solution of 20 g of acrylamide derivative 1 and 60 g of acrylic acid in 50 g of tetra~
hydrofuran and also 20 g of N-vinylpyrrolidone dissolved in 20 g of tetrahydrofuran. At the same time an initiator solution comprising 2 g of 75% strength tert-butyl perpivalate and 30 g of tetrahydrofuran is added dropwise in the course of 40 minutes. The mixture is refluxed for a further hour, cooled down and neutralized with 140 g of 25% strength aqueous sodium hydroxide solution. The tetrahydrofuran is distilled off and the copolymer solution obtained is adjusted to a solids content of 30~
by weight with water. The K value is 48.3 (measured in 1%
strength aqueous solution).
Polymer 29 A 500 ml 4-necked flask equipped with a stirrer, a reflux condenser and 4 metering means is charged with 125 g of tetrahydrofuran, which are heated to the boil.
The content~ are admixed over 2 hours with 53 g of acrylic acid and at the same time with 23 g of acrylamide derivative 4 dissolved in 35 g of tetrahydrofuran and over 2.5 hours with a solutlon of 1.5 g of 2,2'-azobis-(2,4-dimethylvaleronitrile) in 20 g of tetrahydrofuran.
The mixture is refluxed for a further hour and cooled down. The copolymer solution is admixed with 109 g of triethanolamine over 30 minutes and then diluted with lO0 g of water. After the tetrahydrofuran has been distilled off, the mixture is ad~us~ed to a solids content of 40~. The K value (measured in 1~ strength aqueous solution) is 27.8.

- 35 - O.~. 005~/41782 Testing of polymers as detergent additives Test criteria:
Primary detergency and graying Washing machine Launder-o meter Washing temperature 60C
Water hardness 3 mmol of Ca/l = 16.8~ German hardness (ratio Ca:Mg 3:1) Washing time 30 min (including heating-up time) Wash cycles 4 Detergent dose 6 g/l Liquor ratio 14.3:1 Fabrics White fabrics: cotton/polyester weave polyester weave Soil cloth: WFK 20 D (Waschereiforschung Krefeld~
(replaced after every wash~
Whiteness measurement in Elrepho in % reflectance Whiteness of unwashed fabrics:
Cotton/polyester 80.4 Polyester 78.0 WFK 20 D 37.8 The reported figures are the whiteness differen-ces of the individual fabrics before and after the wash.
The higher the whiteness difference on the soil cloth WFK 20 D, the higher the primary detergency.
The imaller the differences on the white fabrics, the better the grayness inhibition.
The test control was a polymer-free detergent formulation.
Liquid detergent:
Formulation A
10~ of sodium dodecylbenzenesulfonate, 50~ strength in water 3% of the reaction product of 1 mol of C13/l5 oxo process alcohol and 7 mol of ethylene oxide 2% of polypropylene glycol MW 600 2 ~
- 36 - O.Z. 0050/41782 77~ of water 8% of polymer according to the present invention Formulation B
13.5% of sodium dodecylbenzenesulfonate, 50% strength in water 17% of the reaction product of l mol of C13/15 oxo process alcohol and 7 mol of ethylene oxide 14% of coconut fatty acid 0.7% of citric acid 7% of triethanolamine 1% of KOH
7% of isopropanol 3% of polypropylene glycol MW 600 8% of polymer according to the present invention 28.8~ of water 2 ~
- 37 - O.Z. OOS0/41782 Testing of polymers in formulation A
Primary detergency and graying The figures reported are in each case the white-ness differences in ~ reflectance between washed and unwashed fabric.

Example If used, Primary Graying No. polymer No. detergency Polyester Cotton/PES

1 1 21.2 7.2 9.8 2 2 20.3 4.0 8.2 3 3 24.3 5.2 10.2 4 4 16.8 3.5 13.7 22.1 3.1 8.5 6 6 21.4 2.8 9.5 7 7 22.4 2.9 11.1 8 8 22.~ 5.2 8.4 9 9 24.2 6.1 10.9 22.7 4.1 12.2 11 11 22.3 4.5 14.2 12 12 26.3 4.3 12.7 13 13 20.8 4.8 13.7 14 14 24.4 2.3 11.6 24.7 3.9 11.7 16 16 26.5 7.7 13.5 17 18 23.~ 8.3 13.7 18 20 17.0 7.5 14.1 Compara-tive without Example 1 addition 11.4 7.8 14.3 2~ 3 ~
- 38 - O.Z. 0050/41782 Testing of polymers in formulation B
Primary detergency and graying The figures reported axe in each case the white-ness differences in % reflectance between washed and unwashed fahric.

Example If used, Primary Graying No. polymer No. detergency Polyester Cotton/PE~

lg 1 18.1 6.2 11.7 2 23.7 11.7 17.5 21 3 23.2 10.6 14.6 22 4 19.3 7.7 16.4 23 5 20.6 6.9 11.3 24 6 20.6 6.7 12.2 7 23.3 6.0 13.5 26 8 21.5 6.2 10.9 27 9 23.8 6.6 11.6 28 10 25.9 6.7 11.9 29 11 22.7 7.5 13.6 12 27.4 6.9 12.7 31 13 21.9 8.4 15.5 32 14 23.0 7.5 15.2 33 15 23.2 8.0 12.2 34 16 24.4 9.0 10.9 18 18.3 8.3 14.7 36 20 21.3 g.0 15.2 37 22 20.1 6.3 10.7 38 23 19.9 7.4 13.1 39 24 18.9 7.3 12.5 21.9 6.7 12.7 41 26 20.3 8.0 10.3 42 27 19.5 8.0 14.0 43 28 19.5 6.6 13.4 44 29 20.3 5.9 14.1 2 ~;3 ~

39 - ~.Z. 0050/41782 Comparative If used, Primary Graying Example No. polymer No. detergency Polyester Cotton/PES

2 without addition 15.8 9.1 15.3 3 addition of 8X of 16 . 5 8 . 7 14 . 7 a reaction product of 7 mol of ethy-lene oxide and 1 mol of C13/15 oxo process alcohol As can be seen from the Examples, the polymers to be used according to the present invention distinctly improve the primary detergency of detergent formulations.
At the same time they produce an improvement in grayness inhibition. The polymers to be used according to the present invention are easy to incorporate in detergent formulations A and B and produce stable, homogeneous solutions.

Claims (7)

- 40 - O.Z. 0050/41782 We claim:

1. The use of a polymer containing as essential monomer at least 5% by weight of N-(alkyloxypolyalkoxy-methyl)carboxamides of monoethylenically unsaturated C3-C8-carboxylic acids having amide groups of the structure -CO-NH-CH2-R, (I) where R =
R1 = C1-C28-alkyl, C3-C28-alkenyl, phenyl or C1-C18-alkyl-phenyl, R2 and R3 are each H, CH3 or C2H5, n is from 1 to 200 and m is from 1 to 100 as copolymerized units, as an addition to low-phosphate and phosphate-free detergents in amounts which increase the primary and secondary detergency of these detergents.

2. A use as claimed in claim 1, wherein the polymer contains (a) from 10 to 99% by weight of N-(alkyloxypolyalkoxy-methyl)carboxamides of monoethylenically unsaturated C3-C8-carboxylic acids having amide groups of the structure I and (b) from, 90 to 1% by weight of other monoethylenically unsaturated monomers as copolymerized units.

3. A use as claimed in claim 1 or 2, wherein the polymer contains as comonomers (b) monoethylenically unsaturated C3-C8-carboxylic acids, esters thereof with C1-C28-alcohols, esters of monoethylenically unsaturated C3-C8-carboxylic acids with reaction products of C1-C28-alcohols and ethy-lene oxide, propylene oxide and/or butylene oxide in a molar ratio of from 1:1 to 1:100, amides, N-C1-C18-alkyloxymethylamides and nitriles of monoethyl-enically unsaturated C3-C8-carboxylic acids, vinyl esters of saturated carboxylic acids of from 1 to 20 carbon atoms, C1-C28-alkyl vinyl ethers, styrene or mixtures thereof as copolymerized units.

4. A use as claimed in claim 1 or 2, wherein the polymer additionally contains as monomer (c) from 0.01 to 20% by weight of compounds having at least two ethyleni-cally unsaturated nonconjugated double bonds, as copoly-merized units.

5. A use as claimed in claim 1, wherein homopolymers of N-(alkyloxypolyalkoxymethyl) carboxamides of monoethy-lenically unsaturated C3-C8-carboxylic acids having amide groups of the structure I or copolymers of these monomers with one another are used.

6. A use as claimed in any one of claims 1 to 5, wherein polymer solutions are used obtainable by poly-merizing the monomers in addition products of alkylene oxides of from 2 to 4 carbon atoms with C1-C28-alcohols or C1-C18-alkylphenols.

7. A detergent containing as essential constituents (1) at least one anionic surfactant, a nonionic surfac-tant or a mixture thereof and (2) from 0.1 to 20% by weight of a polymer containing as essential monomer at least 5% by weight of N-(alkyl-oxypolyalkoxymethyl) carboxamides of monoethyleni-cally unsaturated C3-C8-carboxylic acids having amide groups of the structure -CO-NH-CH2-R, (I) where R = R1-O-(CH-CH-O) n-, R1-O-(CH2-CH2-CH2-CH2-O)m-R1 = C1-C28-alkyl, C3-C28-alkenyl, phenyl or C1-C18-alkyl-phenyl, R2 and R3 are each H, CH3 or C2H5, n is from 1 to 200 and m is from 1 to 100 as copolymerized units.