CA2074747A1

CA2074747A1 - Polymers of ethylenically unsaturated, n-containing compounds, polymerized in the presence of monosaccharides, oligosaccharides, polysaccharides or derivatives thereof

Info

Publication number: CA2074747A1
Application number: CA002074747A
Authority: CA
Inventors: Harald Meyer; Walter Denzinger; Axel Sanner; Rolf-Dieter Reinhardt; Franz Frosch; Hans-Juergen Raubenheimer
Original assignee: Individual
Current assignee: BASF SE
Priority date: 1991-08-03
Filing date: 1992-07-28
Publication date: 1993-02-04
Also published as: DE59207829D1; JPH05194673A; EP0526800A1; DE4125752A1; ES2095988T3; EP0526800B1

Abstract

O.Z. 0050/42582 Abstract of the Disclosure: Polymers of ethylenically unsaturated compounds which contain one or more covalent-ly bonded nitrogen atoms in the molecule, polymerized in the presence of monosaccharides, oligosaccharides, poly-saccharides or derivatives thereof, are obtainable by free radical copolymerization of (A) monomers or monomer mixtures selected from the group consisting of (a) N-vinylimidazoles which may be substituted in the heterocyclic ring by not more than three C1-C12-alkyl radicals and may he present in the N-quaternized form or in salt form, (b) five-membered to eight-membered N-vinyllactams which may be substituted in the ring by not more than three C1-C12-alkyl radicals, (c) dialkylaminoalkyl acrylates or methacrylates where the dialkylaminoalkyl radical has a total of not more than 30 carbon atoms and which may be present in the N-quaternized form or in salt form, (d) N-(dialkylaminoalkyl)-acrylamides or -meth-acrylamides where the dialkylaminoalkyl radical has a total of not more than 30 carbon atoms and may be present in the N-quaternized form or in salt form and (e) diallyl-C1-C12-alkylamines or salts thereof or diallyldi-(C1-C12-alkyl)-ammonium compounds, further comonomers (A) which may be present being (f) monoethylenically unsaturated C3-C10-carboxylic acids and alkali metal, alkaline earth metal or ammonium salts thereof, (g) monoethylenically unsaturated C3-C10-carbox-ylates and (h) small amounts of compounds which contain two or more ethylenically unsaturated, non-conjugated double bonds in the molecule, in the presence of O.Z. 0050/42582 (B) monosaccharides, oligosaccharides, polysaccharides, thermally or mechanically treated, oxidatively, hydrolytically or enzymatically degraded poly-saccharides, oxidized hydrolytically degraded or enzymatically degraded polysaccharides, chemically modified mono , oligo- or polysaccharides or mix-tures of the stated compounds (B) in a weight ratio (A) : (B) of (95 to 20) : (5 to 80).
The polymers are suitable as film-forming con-ditioners in cosmetic formulations and as stabilizers for perfumes and perfume oils.

Description

2~374~7~r~
oOz. 0050/~2582 Polymers o~ ethylenically unsaturated, N-containina compounds, polymerized in the presence_of _nosaccharides, oliqo~accharid_s, po~ysacchar-ldes or derivatiyes thereof The present inv~ntion relate~ to novel polymers of ethylenically unsaturated, N-containing compounds which are polymerized in the pr~sence of monosaccharides, oligosaccharides, polysaccharides or derivatives thereof.
The present invention urthermore relates to a process for the preparation of these polymers and their various uses.
Polymers or copolymers of, for example, N-vinyl-lactams, N-vinylimidazoles or N-vinylimidazolinium salts and dialkylaminoalkyl (meth)acrylates or -(meth)acryl-amides or quaternization products thereof have long been used in the cosmetic~ sector.
For example, DE C 36 17 069 (1) discloses homo-polymers of 3-alkylvinylimidazolium chlorides and copoly-merR of vinyllactams with 3-alkylvinylimidazolium chlor-ides, which are used as hair conditioners and can be obtained by free radical polymerization in aqueous and aqueous alcohol solutions at from 40 to 100C.
US-A 3 9~0 86~ (2~ discloses quaternary copoly-mers which consist of from 20 to 95 mol % of vinyl-pyrrolidone, from 5 to ao mol % of dialkylaminoalkyl acrylates or methacrylates and from 0 to 50 mol % of a monomer which is copolymeri~able with vinylpyrrolidone, said copolymers heing present as an aqueous, alcoholic or aqueous alcoholic solution and being used in cosmetic compositions.
WO 90~01920 (3) describes copolymers of N-(dialkylaminoalkyl)acrylamides or -methacrylamides or quaternization products thereof with vinyllactam~. The water-soluble copolymer~ obtained are u~ed for hair and skin care.
However, these prior art polymers have a number of disadvantages. For ex~mple, their water absorption is 2 ~ 7 l~ 7 - 2 - O.Z. 0050/42582 still too hiyh and the compatibility with anionic surfac-tants still too lo~. In co~metic hair formulations, ~or example, the wet combability of the hair and -the care effect generally are still unsatisfactory.
Complexes of poly-N-vinylpyrrolidone with iodine, ie. iodophores, are widely used as fine disinfectants.
Complexes which are stahle during storage are obtained as disclosed in U.S. Patent 4,027,083 only when the polymer is prepared in an expenRive manner in anhydrous solvents, which have to be substantially removed after the polymerization.
DE-A 27 42 595 disclo~es graft copolymers o~
starch and N-vinylpyrrolidone which are obtained by polymerization with the redox initiator Mn3t. Products containing heavy metals have the disadvantage that they cannot be used in many applications owing to the heavy metal content.
U.S. Patent 4,131,576 describes graft copolymers of starch and water-soluble monomers, which are obt~ined by polymerization in suspension and are isolated as a solid. It is known that the degrees of grafting in polymerizations carried out in this manner are very low.
It is an object of the present invention to provide novel agents which do not have the disadvantages of the prior art.
We have found that this object is achieved by polymers of ~thylenically unsaturated compounds which contain one or more covalently bonded nitrogen atoms in the molecule, polymerized in the presence of monosac-charides, oligosaccharides, polysaccharides or deriva-tives thereof, which are obtainable by polymerization, initiated with free radical initiators, in liquid systems of (A) monomers or monomer mixtures selected from the group consisting of (a) N-vinylimida~oles which may be substituted in the heterocyclic ring by not more than three .

287~7~7 _ 3 _ o.z. 0050/42582 c1-c12 alkyl radicals and may be present in N-quaternized form or :Ln salt form, (b) five-membered to eight-membered N-v.inyllactams which may be substituted in the ring by not more than three C1-C1~-alkyl radicals, (c~ dialkylaminoalkyl acrylates or methacrylates where the dialkylaminoalkyl radical has a total o~ not more than 30 carbon atoms and which may be present in N-quaternized form or in salt form, (d) N-(dialkylaminoalkyl)-acrylamides or -meth-acrylamides where the dialkylaminoalkyl radical has a total of not more than 30 carbon atoms and which may be present in N-quaternized form or in salt form and (e) diallyl-C~-Cl2-alkylamines or salts thereof or diallyldi-(Cl-Cl2-alkyl)-ammonium compounds, further comonomers (A) which may be present being (f) monoethylenically unsaturated C3~C10-carboxylic acids and alkali metal, alkaline earth metal or ammonium salts thereof, (g) monoethylenically unsaturated C3-C10-carbox-ylates and (h) small amounts of compounds which contain two or more ethylenic~lly unsaturated, nonconjugated double bonds in the molecule, in the presence of (~) monosaccharides, oligosaccharides, polysaccharides, thermally or mechanically treated, oxidatively, hydrolytically or enzymatically degraded poly-saccharides, oxidized hydrolytically or enzymatical-ly degraded polysaccharides, chemically modified mono-, oligo- or polysaccharides or a mixture of the stated compounds (B) in a weight ratio ~A) : (B) of (95 to 20) : (5 to 80), in particular (75 to 40) : (25 to 60)~
Examples of N-vinylimidazoles (a) are :
, ' ~ :

2~7~7~7 - 4 o.z. 0050/42582 unsubstituted 1-vinylimidazole, 2-methyl 1 vinylimidazole, 4-methyl-1-vinylimidazole, 2,4-dimethyl-1-vinylimidazole and 2-ethyl-1-vinylimidazole.
Particularly suitable straight-chain or branched C~-C12-alkyl radicals ai substituents in the ring system of the compounds ~a) and al30 as substituents in the compounds (b) and (e) are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, as well as n-pentyl, isopentyl, n-hexyl, n-heptyl, n octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, isoundecyl or n-dodecyl.
Examples of quaternized N-vinylimidazoles (a) are 1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium chlorider 3-methyl-1-vinylimidazolium ~romide, 3-methyl-l-vinylimidazolium iodide, 2,3-dimethyl-1-vinylimidazol-ium chloride, 3-n-dodecyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methylsulfate, 3-ethyl-1-vinylimidazolium ethylsulfate, 2,3~dimethyl-1-vinyl-imidazolium sulfate and 2-methyl-3-ethyl-1-vinylimidaæol-ium ethylsulfate.
Counter-ions for the quaternized compounds or salts (a) as well as for the quaternized compounds or salts (c), (d) and (e) may be in particular halides, ie.
fluoride, bromide, iodide and in particular chloride, acetate, lactate, bisulfate, sulfate, mono- or dialkyl-sulfate, eg. methylsulfate or dimethylsulfate, sulfonates, bisulfite or sulfite.
Particularly suitable quaternizincJ agents are dialkyl sulfates, eg. dimethyl sulfate, diethyl sulfate or methyl sulfate, alkylsulfonic acids, eg. methyl-sulfonic acid or ethylsulfonic acid, benzyl halides, eg.
benzyl chloride, benzyl bromid~ or benzyl iodide, alkyl halides, eg. methyl chloride, ethyl bromide, ethyl chloride, octyl chloride or stearyl chloride, chlorine-containing lactams, eg. N-chloromethylpyrrolidone or N-chloroethylc:aprolactam, heterocyclic sulfates, eg. 1,2-oxathiethane-2,2 dione, lactones, eg. ~-propiolactone or 2~7~ 7 - 5 - O.Z. OOS0/42582 y-butyrolactonel and carbonic eskers, eg. dimethyl carbonate, methylethyl carbonate or diethyl carbonate.
To convert the basic monomers (A) into their salts, the corre~ponding acids, eg. hydro~hloric acid, acetic acid or sulfuric acid, are advantageously used.
Five-membered to eight-membered N-vinyllactams (b) are, for example, 1-vinylpyrrolidone, 1-vinyl-caprolactam, 1-vinylpiperidone, 4-methyl-1-vinyl-pyrrolidone, 3,5-dimethyl-1-vinylcaprolactam and 1-vinyloctahydro-2-azoquinone.
Examples of suitable dialkylaminoalkyl (meth)acrylates (c) having a total of up to 30, in particular up to 22, carbon atoms in the dialkylaminoalkyl radical are:
dimethylaminoethyl acrylate, methylethylaminoethyl acrylate, dimethylaminomethyl methacrylate, diethylamino-ethyl acrylate, diethylaminoethyl methacrylate, dimethyl-aminoethyl acrylate, dimethylaminoethyl methacrylate, methylethylaminoethyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, dimethylamino-amyl methacrylate, diethylaminoamyl methacrylate, di-methylaminohexyl acrylate, diethylaminohexyl meth-acrylate, dimethylaminooctyl acrylate, dim~thylaminooctyl methacrylate, diethylaminooctyl acrylate, diethylamino-octyl mekhacrylate, dimethylaminododecyl methasrylate,diethylaminolauryl acrylate, diethylaminolauryl meth-acrylate, dimethylaminostearyl acrylate, dimethylamino-stearyl methacrylate, diethylaminostearyl acrylates, diethylaminostearylmethacrylate,di-tert-butylaminoethyl methacrylate and di-tert-butylaminoethyl acrylate and quaternization products thereof and salts thereof.
Examples of suitable N-(dialkylaminoalkyl)-(meth)acrylamides (d) having a total of up to 39, in particular up to 22, carbon atoms in the dialkylamino-alkyl radical are:
N-[3-(dimethylamino)propyl]acrylamide, N [3-(dimethyl-amino)propyl]methacrylamide, N-[3-(diethylamino)propyl]-:: :

2~7~7~7 - 6 - O.Z. 0050/42582 acrylamide, N-[3-(diethylamino)propyl]methacrylamide, N-~l~-(dimethylamino)dodecyl]methacrylamide~ N-[12-(di-methylamino)dodecyl]acrylamide~, N-~18-(dimethylamino)-octadecyl]methacrylamide, N-[18-(dimethylamino)octa-decyl]acrylamide, N-[8-(dimethylamino)octyl]methacryl-amide, N-[8-(dimethylamino)octyl]acrylamide, N [7-(di-methylamino)heptyl]methacrylamide, N-[7-(dimethylamino)-heptyl]acrylamide, N-[14-(dimethylamino)tetradecyl]meth-acrylamide, N-[14-(dimethylamino)tetradecyl]acrylamide, ~-[4~(dimethylamino)butyl]methacrylamide, N-[4-(dimethyl-amino)butyl]acrylamide, N-[4-(diethylamino)butyl]meth-acrylamide, N-[4 (diethylamino)butyl]acrylamide, N-[3-(methylethylamino)propyl]methacrylamide, N-[3-(methyl-ethylamino)propyl]acrylamide, N-[3-methyl-5-(climethyl-amino)pentyl]acrylamide, N-[~-methyl-5-(dimethylamino)-pentyl]methacrylamide, N-[2-methyl-4-(dimethylamino)-butyl]acrylamide or N-[2-methyl-4-(dimethylamino)butyl]-methacrylamide and quaternization products thereof and salts thereof.
2~ For example, the following compounds may be used as diallyl-C1-Cl2-alkylamines or salts thereof and as diallyldi-(Cl-C12-alkyl)-ammonium compounds (e):
hydrochlorides, hydrobromides, hydriodides, acetates, lactates, bisulfates and bisulfites of methyldiallyl-amine, ethyldiallylamine, butyldiallylamine, octyl-diallylamine, decyldiallylamine or doclecyldiallylamine;
dimethyldiallylammoniumchloridejdimethyldiallylammonium bromide, methylethyldiallylammonium chloride, methyl-ethyldiallylammonium hromide, methylbutyldiallylammonium chloride, methylbutyldiallylammonium bromide, methyl-dodecyldiallylammonium chloride or methyldodecyldiallyl-ammonium bro:mide.
Monoethylenically unsaturated C3-Cl0-carboxylic acids and alkali metal, alkaline earth metal or ammonium salts thereof may be used as comonomers (f), for example acrylic acicl, methacrylic acid, dimethylacrylic acid, ethylacrylic acid, allylacetic acid, vinylacetic acid and , ,,, 2~7~7~7 - 7 o.z. 0050/~2582 vinylpropionic acid. From this group, acrylic acid, methacrylic acid, mixtures thereof and the sodium, potassi~m, calcium or ammonium salts or mixture~ thereof are preferably used.
Comonomer~ (g) used are, for example, alkyl, hydroxyalkyl and vinyl esters~ such as methyl acrylate, ethyl acrylate, n butyl acrylate, n-butyl methacrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacry-late, hydroxypropyl methacrylate, vinyl formate, vinyl acetate, vinyl propionate and mixtures thereof. The number of carbon atoms in the alkyl or hydroxyalkyl radical i3 preferably not more than 18, in particular not more than 12.
The comonomers (f) and (g) always occur together with one or more monomers (a) to (e) and serve mainly for modifying the novel polymers. The comonomers (f) and (g) are usually used in amounts of from 5 to 95, in par-ticular from 20 to 80, % by weiqht, based on the total amount of all monomers (A).
Further modification of the novel polymers can be achieved if the monomer or monomer mixtures contain not more than 5% by weight of a comonomer (h) having two or more ethylenically unsaturated, nonconjugated double bonds in the molecule. If the compounds (h) are present, the preferably used amount is from 0.05 to 2% by weight, based in each case on the total amount of all monomers (A).
The presence of the comonomers (h) during the polymerization results in an increase in the K value of the copolymers. Suitable compounds of this type are, for example, esters of (meth)acrylic acid with polyhydric alcohols, eg. glycol diacrylate, glyceryl triacrylate, glycol dimethacrylate, glyceryl trimethacrylate and polyols which are diesterified or polyesterified with acrylic acid or methacrylic acid, such as pentaerythritol and glucose. Other suitable cro~slinking agents of this 2 0 7 ~ 7 l~ J

- 8 - O.Z. 0050/42582 type are divinylbenzene, divinyldioxane, pentaerythrityl triallyl ether and pentallylsucrose. From this group of compounds (h), water-soluble comonomers, such as glycol diacrylate and glycol diacrylates of polyethylene glycols having molecular weights of not more than 3000 g/mol, are preferably used.
In a preferred embodiment, either the compounds (a), (c), (d) or (e) alone or mixtures of from 5 to 95%
by weight of a compound (b) and from 95 to 5% by weight of one or more of the monomers (a), (c), (d), (e), (f), (g~ and (h) are used as monomers (A), (h) being employed in an amount of not more than 5% by weight, based on the total amount of all monomers (A).
The polymerization of the monomers (A) is carried out in the presence of natural substances based on monosaccharides, oligoqaccharides, polysaccharides or derivatives thereof (B). These natural substances are, for example, saccharides of vegetable or animal origin or products of the metabolism of microorganisms and syn-thesis and modification products thereof, which are already dispersible or soluble in water, alkalis or acids or, during the polymerization, become dispersible or soluble directly or in a form partially or completely neutralized with acids, alk~lis, amines or ammonia.
These are, for example, pectin, algin, chitin, chitosan, heparin, carrageenan, agar, gum arabic, tragacanth gum, karaya gum, ghatti gum, carob bean powderr guar gum, tara gum, inulin, xanthan, dextran, nigeran and pentosAns, such as xylan and araban, the main components of which consist of D-glucuronic acid, D-galacturonic acid, methyl D-galacturonate, D-mannuronic acid, L-guluronic acid, D- and L-galactose, 3,6-anhydro-D-galactose, arabinose, L-rhamnose, D~xylose, L-fucose, D-mannose, D-fructose and D-glucose, 2-amino-2--deoxy-D-glucose and 2-amino-2-deoxy-D-galactose and the N-acetyl derivatives thereof.
From the economic point of view, starches, ~7~74 7 _ g - o.z. 0050/42582 thermally and/or mechanically treated starches, oxida-tively, hydrolytically or enzymatlcally degraded star-ches, oxidized hydrolytically degraded starches or oxidized enzymatically degraded starches, and chemically modified starches and chemically modified monosaccharides and oligosaccharides are preferably used a~ components (~) in the polymerisation. In principle, all starches are suitable. However, starches of corn, wheat, rice and jopioku and in particular potato ~tarch are preferred.
The starches are virtually insoluble in water and can be converted into a water-soluble form in a known manner by thermal and/or mechanical treatment or by enzymatic or acid-catalyzed degradation.
Exampl~s o-f starch degradation product~ which are obtainable by oxidative, hydrolytic or enzymatic degrada tion of starch are the following compounds: dextrins, such as white and yellow dextrins, maltodextrins, glucose syrup, malto syrup, hydrolysis products having a high content of D-glucose, and maltose and D-glucose and their isomerization product fructose. Other suitable com-ponents (B) are mono- and oligosaccharides, such as galactose, mannose~ ribose, sucrose, raffinose, lactose and trehalose, and degradation products of cellulose, for example cellobiose and oligomPrs thereof.
Colorl~ss or only ~lightly yellow aqueous solu-tions of the novel polymers are obtained in particular when ~tarches degraded under acid catalysis or enzymatic-ally are used a~ components (B). Such desrad~d starche are commercially available as starch conversion products.
They contain from 0.5 to 95, preferably from 8 to 20, %
by weight of maltose, from 2 to 90% by weight o mal-totriose and higher sugars.
Other suitable components (B) are oxidiæed starches, for example dialdehyde starch, and oxidized starch degradation products, for example gluconic acid, glucaric acid and glucuronic acid. Such compounds are obtained, ~or example, by oxidation of ~tarch wi~h , , .

2D 7~ 7l17 - 10 - O.Z. 0050/~2582 periodate, chromic acid, hydrogen peroxide, nitrogen dioxide, nitrogen tetroxide, nitric acid and hypochlorite.
Suitable components (B) are furthermore chemical-ly modifled polysaccharides, in particular chemically modified starches, for example starch degradation pro-ducts and starches converted with acids into esters and with alcohols into ethers. The esteri-fication of these substances is possible both with inorganic and with organic acids, their anhydrides or halides. In the case of direct esterification, the water liberated leads to acid-catalyzed cleavage o~ glycosidic bonds. Phosphated and acetylated starches and starch degradation products are of particular industrial interest~ The mo~t common method for etherifying starch is the treatment of the starch and of the starch degradation products wikh organic halogen compounds, epoxides or sulfates in aqueous alkaline solution. Starch ethers are, for example, the alkyl ethers, hydroxyalkyl ethers, carboxy-alkyl ethers and allyl ethers of starch. Chemically modified starches for component (B) are also understood as meaning cationically modified starches, for example starches reacted with 2,3-epoxypropyltrimethylammonium chloride.
Chemically modified polysaccharides include, for example, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylhydroxyethylcellu-lose, sulfoethylcellulose, carboxymethylsulfoethylcellu-lose, hydroxypropylsulfoethylcellulose, hydroxyethyl-sulfoethylcellulose, methylsulfoethylcellulo~e and ethylsulfoethylcellulse.
Other suitable components (B) are chemically modified degraded starches, for example hydrogenation product~ of starch hydrolysis products, such as sorbitol and mannitol, maltitol and hydrogenated glucose syrup or oxidized hyclrolytically degraded starches or oxidized enzymatically clegraded starches.

2~7~7 ~ O.Z. 0050/~2582 The products of the acid-catalyzed or enzymatic reglycosidation or glycosidation, for example methyl-glucoside, are also suitable.
For the preparation of the novel polymers, the monomers (A) are subjected to free radical polymerization in the presence of the compounds (B). In some case~, it may be advantageous for khe action of the resulting polymer to use two or more of the compounds stated under (B), for example mixture~ of a monosaccharide and an oligosaccharide, mixtures of an enzymatically degraded starch and a mono~accharide or mixtures of glucose and sucrose or mannose.
The polymerization can be carried out in the presence or absence o~ inert solvents or inert diluents.
Since the polymerization in the absence of inert solvents or diluents generally leads to different polymers, the polymerization is preferably carried out in an inert solvent or diluent. Examples of suitable inert diluents are those in which the compounds stated under ~B) can be suspended, and those which dissolve the monomers (A). In these cases, the polymers are present in suspended form after the reaction and can readily b0 isolated in solid form by filtration. Examples of suitable inert diluents are toluene, o-, m- and p-xylene and isomer mixture~
thereof, ethylbenzene, aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane, cyclooctane or methylcyclohexane, and mixture3 of the stated hydrocarbons or benzene fractions which contain no polymerizable monomers. Chlorohydrocar-bons, such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane and ketrac~loroethane, are also suitable. In the procedure describedr in which the compounds (B) are suspended in an inert diluent, anhydrous compounds 5B) are preferably used.
A preferred method for the preparation of the polymers is solution polymerization, the compounds (B), the monomers (A) and the polymer formed being present at . ~ :
:

:

2~7~
- 12 - O.Z. 0050/42582 least in dispersed form, preferably in dissolved form.
For example, inert solvents, such as methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tetra-hydrofuran and dioxane, and mixtures of the stated inert solvents are suitable for the solution polymerization.
The polymerization can be caxried out continuously.
As stated above, components (A) and (~) can al90 be polymerized in the absence of inert diluents or solvents. In particular, continuous polymerization at from 160 to 250C i suitable ~or this purpose. In some cases, it is possible to carry Ollt the procedure in the absence of polymerization initiators. However, catalysts which form free radicals under the polymerization conditions, for example inorganic and organic peroxides, persulfates, azo compounds and redox catalysts are preferably used here too.
The novel products, which are obtained by poly-merization of components (A) and (B), are generally prepared in the presence of free radical initiators.
Preferred free radical initiators are all compounds which have a half life of less than 3 hours at the polymeriza-tion temperature selected in each case. If the polymer-ization is started at a low temperature and completed at a higher temperature, it is advantageous tv employ two or more initiators which decompose at different tempera-tures, ie. first to use an initiator which decomposes at a lower temperature for the tart of the polymerization and then to complete the main polymerization using an initiator which decomposes at a higher temperature.
Water-soluble or water insoluble initiators or mixtures of water-soluble and water-insoluble initiators may be used. In this case, the water-insoluble initiators are soluble in the organic phase.
For the temperature ranges stated below, for example, th~ stated initiator~ may be used.
Temperature: 40 to 60C
Acetylcyclohexanesulfonyl peroxide, diacetyl peroxy-2 ~ 7 d~ 7 - 13 - o.zO 0050/42582 dicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethyl-hexyl peroxydicarbonate, tert-butyl perneodecanoate, tert-amyl perneodecanoate, 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-~2-amidinopropane) dihydrochloride or 2,2'-azobis-[2-(2-imidazolin-2-yl)-propane] dihydrochloride;
Temperature: 60 to 80C
tert-Butyl perpivalate, tert-amyl perpivalate, dioctanoyl peroxide, dilauryl peroxide or 2,2'-azobis-(2,4-dimethyl-valeronitrile);
Temperature: 80 to 100C
~ibenzoyl peroxide, tert-butyl per-2-ethylhexanoate, tert-butyl permaleate, 2,2'-azobisisobutyronitrile, dimethyl-~,2'-azobisisobutyrate, sodium persulfate, potassium persulfate or ammonium persulfate;
Temperature: 100 to 120C
Bis-(tert-butylperoxy)-cyclohexane~ tert-butylperoxyiso-propyl carbonate, tert-butyl peracetate or hydrogen peroxide;
Temperature: 120 to 140C
2,2-Bis-(tert-butylperoxy)-butane, dicumyl peroxide, di-tert-amylperoxide or di-tert-butyl peroxide;
Temperature: ~ 140C
p-Menthane hydroperoxide, pinane hydroperoxide, cumene hydroperoxide and tert-butyl hydroperoxide.
If salts or complexes o heavy metals, for example copper, cobalt, manganese, iron, vanadium, nickel or chromium salts, or organic compounds, for example benzoin, dimethylaniline or ascorbic acid, are used in addition to the stated initiators, the half lives of the stated free radical initiators can be reduced. For example, tert-butyl hydroperoxide may be activated with the addition of 5 ppm of copper(III) acetylacetonate to ~uch an extent that polymerization may be effected at as low as 100C.
The reducing component of redox catalysts may be formed, for example, from compounds such as sodium 2 ~ 7 ~ 7 - 14 - O.Z. 0050/425~2 sulfite, sodium bisulfite, sodium formaldehyde sulfox~
ylate or hydrazine.
Based on the monomers (A) used in the polymeriza-tion, from 0.01 to 20, preferably from 0.05 to 10, % by weight of a polymerization inltiator or of a mixture of a plurality of polymerization initiators are used, and from 0.01 to 15~ by weight of the reducing compounds are added as redox components. Heavy metals are used in the range from 0.1 to 100 ppm, preEerably from 0.5 to 10 ppm.
It is often advantageous to use a combination of perox-ide, reducing agent and heavy metal a the redox catalyst.
The polymerization of components (A) and (B) can also be carried out by the action of ultraviolet radia-tion, in the presence or absence of W initiators. Forthe polymerization under the action of UV radiation, the conventional suitable photoinitiators or sensitizers are used. These are, for example, compounds such as benzoin or benzoin ethers, ~-methylbenzoin or ~-phenylbenzoin.
Triplet sensitizers, such as benzyl diketals, can also be used. W radiation sources which are used are, for example, high energy W lamps, such as carbon arc lamps, mercury vapor lamps or xenon lamps, as well as low- W
light sources, such as fluorescent tubes having a high blue content.
In order to prepare products having a low K
value, the polymerization is advantageously carried out in the presence of regulators. Examples of suitable re~ulators are mercapto compounds, such as mercapto-ethanol, mercaptopropanol, mercaptobutanol, mercapto-acetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan. Other suitable regulators are allyl compounds, such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyral-dehyde and isobutyraldehyde, formic acid, ammoniumformate, propionic acid, hydrazine sulfate and butenols.
If the polymerization is carried out in the presence of 2~7~7~7 - 15 - O.z. 0050/42582 regulators, from 0.05 to 20~ by weight, based on the total amount of the monomers (A) used in the polymeriza-tion, of said regulators are required.
The polymerization is usually effected in an inert gas atmosphere in the absence of atmospheric oxygen. During the polymerization, thorough mixing of the reactants is generally ensured. In the case of relatively small batches where reliable removal of the heat of polymerization is ensured, the reactants, which are preferably present in an inert diluent, can be polymerized by a batchwise method, by heating the reac-tion mixture to th polymerization temperature. These temperatures are as a rule from 40 to 180C.
In order to be able better to control the course of the polymerization reaction, the monomers (A) are added continuously or batchwise to the polymerizing mixture after initiation of the polymerization, at a rate such that the polymerization is readily controllable in the desired temperature range in the presence of com-ponents (B). Preference is given to a method of addingthe monomers (A) in which first some or all of the compounds (B) toyether with one or more monomers (A) are initially taken in the polymerization reactor and are heated therein to the desired polymerization temperature while stirring~ As soon as this temperature ha- been reached, khe monomers (A) and the initiator and, where relevant, the remainder of component (B) and if nece~ary a regulator are added over a period of from about 1 to 10, preferably from 2 to 8, hours. Such a procedure is used, for example, in the polymerization of component~
(A) and (B) in an inert diluent in which the component (B) is suspended, and also in the polymerization carried out in solution.
The novel polymers are preferably prepared by suspension or solution polymerization of the components (A) and (B) :Ln an aqueous medium, solution polymerization in water being particularly preferred. In the solution 2~7~

- 16 - O.Z. 0050/42582 polymerization in an aqueous medium, for example, some of the monomers (A) and some or all of the compounds (B) are initially taken in an aqueous medium and the remainder of the monomexs (A) and, where relevant, the remainder of compound (B~ ~re added continuously or batchwise to the polymerizing reaction mixture.
As stated above, the monomers (A~ can be polymer-ized in aqueous suspension in the presence of poly-saccharides. The polymer~ obtained from polysaccharides are preferably prepared by converting a water-insoluble polysaccharide, initially in aqueou~ suspension, into a water-soluble form with the addition of enzymes and/or acids, and mixing the resulting aqueous solution of the degraded polysaccharide with monomers (A) in order to polymerize these in the presence of the degraded poly saccharide. First a water-insoluble polysaccharide, for example potato starch, is suspended in water and degraded. This degradation may be effected in known manner with the action of enzymes, for example ~- or ~-amylose, or of dsbranching enzyme , eg. pullulanase, or by the action of organic or inorganic acidq. Examples of suitable inorganic acids are phosphoric acid, sulfuric acid, hydrochloric acid and nitric acidO Suitable organic acid~ are, for example, saturated or unsaturated carboxylic acids, such as formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, p-toluenesulfonic acid and ben-zenesulfonic acid.
The enzymatic degradation of starch is usually carried out at from 30 to 120C, while the hydrolytic degradation of starch is effected as a rule at from 50 to 150C. From a~out 5 minutes to 10 hours are re~uired for the hydrolytic degradation, the degree of hydrolytic degradation of the starch depending on the temperature chosen, the p~ and the time. The technical literature provides further information on the degradation of starch. In some cases, it has proven advantageous -to 2 ~ 7 ~ 7 - 17 - O.Z. 0050/42582 use, in the enzymatic or hydrolytic degradation of the starch, one or more of the phosphoru~ compounds which, according to EP-A 175 317, lead to polymers which have very little or no color.
5In the polymerization of components (A) and (B), the temperatures are usually from 40 to 180C, preferably from 50 to 140C, particularLy prefexably from 60 to lOO~C. As soon as the temperature in the polymerization is above the boiling points of the inert diluent or 10solvent or of the monomers (A), the polymerization i5 carried out under superatmospheric pressure. The con-centration of the components (A) and (B) in the polymer-ization in the presence of inert solvents or inert dilu-ents i~ from 10 to 80, preferably from 20 to 70, % by weight.
The preparation of the novel polymers may be carried out in a conventional polymerization apparatus.
For example, stirred kettles equipped with anchor, paddle or impeller stirrers or multistage pulse counter-current 20agitators are used for this purpose. Particularly in the absence of diluents, it may be advantageous to carry out the polymerization in a kneader. It may also be neces-sary to effect polymerization in a kneader when high concentrations are u~ed or when the natural substances 25(B) are high molecular weight ones and initially swell considerably.
Polymers which, where they are soluble in water, have K values of from 8 to 350, preferably from 10 to 250 (measured in 1~ strength by weight aqueous solutions of 30the polymer~ at pH 7 and 25C), are obtained. If the measurements are carried out in 0.1% strength aqueous solutions at pH 7 and 25C, the K valueæ are from 8 to 450, preferably from 10 to 350. The products which can be prepared by the abovementioned processes are from 35colorless to yellowish. In the case of polymerization in an aqueous medium, they are in the form of dispersions or polymer solutions. Low-viscosity to pasty aqueous 2~7~747 - 18 - O.Z. 00~0/42582 solutions or aqueous disper~ions are obtained, depending on the particular composition of the polymers.
. To improve the properties of the novel polymer~, it may be advantageous in some cases subsequently to subject the resulting products to an oxidative tr~atment.
For this purpose, oxidizing agents are allowed to act either directly on the polymer powders or on suspensions of the resulting products in an inert suspending agent or on solutions of the resulting products in an inert solvent, for example in a monohydric alcohol, such a methanol, ethanol, n-propanol or isopropanol, or prefer-ably water or in a mixture o~ water and an alcohol. The oxidation is preferably carried out in aqueous solutions of the products obtained.
Suitable oxidizing agents are those which liberate oxygen when haated alone or in the presence of catalysts. Suitable organic compounds are generally peroxides, which very readily eliminate active oxygen.
At low temperatures, only hydroperoxides and peracids have a substantial oxidizing effect; pereYters, diacyl peroxides or dialkyl peroxides act only at higher tem-peratures. Suitable peroxides are, for example, diacetyl peroxide, isopropyl percarbonate, tert-butyl hydroperox-ide, cumene hydroperoxide, acetylacetone peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, dilauryl peroxide, tert-butyl perpivalate, tert-amyl p~rpivalate, tert-butyl perethylhexanoate, tert-amyl perethyl-hexanoate, tert-butyl perneodecanoate and tert-amyl perneodecanoate.
~he economical inorqanic oxidizing agents which are particularly suitable for the oxidation of aqueous solutions of carbonyl-containing polymeræ are preferred.
Examples are chlorine, bromine, iodine, nitric acid, sodium permanganate, potassium chloratP~ sodium hypo-chlorite, sodium perborate, sodium percarbonate and sodium persulfate. A particularly preferred oxidizing agent is hydrogen peroxide.

~07~7~7 - 19 - O.Z. 0050/425~2 The decomposition of the per compounds, ie. the oxidation, can be forced by the addition of accelerators or activators. These accelerators or actiYators are reducing substances, for example tertiary amines, sul-finic acids, dithionites, sulfites, ~- and ~-ketocarbox-ylic acids, glucose derivatives and heavy metals, prefer-ably in the form of soluble sa]ts of inorganic or organic acids or complexe~. Specifi.c examples are dimethyl-aniline, dimethyl-p-toluidine, diethylaniline, ~odium dithionite, sodium sulfite, ascorbic acid, glucose, pentaacetylglycose~ iron(II) ammonium sulfate, copper(I) chloride and the acetylacetonates of iron, copper, cobalt, chromium, manganese, nickel and vanadium.
The oxidizing agents are advantageously added in amounts of from 1 to 50, preferably from 5 to 30, % by weight, based on the sum of the components (A) and (B).
The reducing agent~ are employed in amounts of from 2 to 50% by weight, based on the oxidizing agents. The heavy metal compound~ are used in amounts of from 0.1 to 100 ppm, preferably ~rom 0.5 to 10 ppm, calculated as heavy metal and based on the polymer~ of (A) and (B). For accelerating the reaction it iR often advantageous, particularly when low temperatures are employed, to add not only reducing agents and but also heavy metal com-pound to the per compound~.
The reaction temperature for the oxidation may ~e from 20 to 150C, preferably from 50 to 120C. It iq sometim~s also advantageous to accelerate the oxidation by exposure to W light or to effect oxidation at low temperatures and for a short time. This ensures that the K value of the novel ~olymer is not markedly decreased.
Air and oxygen, alone or in combination with oxidixing agents, may also be used for oxidizing the products obtained according to the invention.
The present invention furthermore relates to a process for the preparation of polymers of ethylenically unsaturatedcompounds whichcontain one or more covalently 2~7~7'~7 - 20 - O.Z. OOS0/42582 bonded nitrogen atoms in the molecule, polymerized in the presence of monosaccharides~ oligosaccharides, poly-saccharLdes or derivatives thereof, wherein (A) monomers or monomer mixtures selected from the group consisting of (a) N-vinylimidazoles which may be substituted in the heterocyclic ring by not more than three C1-C12 alkyl radical~; and may be present in the N-quaternized form or in salt form, (b) five-membered to ei~ht-membered N-vinyllactams which may be substituted in the xing by not more than three Cl-C12-alkyL radicals, (c) dialkylaminoalkyl acrylates or methacrylates where the dialkylaminoalkyl radical has a total lS of not more than 30 carbon atom~ and which may be present in the N-quaternized form or in salt form, (d) N-(dialkylaminoalkyl)-acrylamide~ or -meth-acrylamides where the dialkylaminoalkyl radical has a total of not more than 30 carbon atoms and which may be present in the N-quaternized form or in ~alt form and (e~ diallyl-Cl-Cl2-alkylamines or salts thereof or diallyldi-(C1-Cl2-alkyl)-ammonium compounds, fllrther comonomer~ (A) which may be present being (f) monoethylenically unsaturated C3-C10-carboxylic acid~ and alkali metal, alkaline earth metal or ammonium salt thereof, (g) monoethylenically unsaturated C3-C10-carbox-ylates and (h) small amounts of compounds containing two or more ethylenically unsaturated, nonconjugated double bonds in the molecule, are subjected to free radical polymerization in the presenc:e of (B) monosacchaxides, oligosaccharides, polysaccharides, thermally or mechanically treated, oxidatively, , ~07~7~

- 21 - o.z. 005~/42582 hydrolytically or enzymatically degraded poly-saccharide~, oxidized hydrolytically degraded or enzymatically de~raded polysaccharides, chemically modified mono-, oligo- or polysaccharides or mix-tures of the stated compound~ ( B ) in a weight ratio (A) : (B) of (95 to 20) : (5 to 80).
The novel polymers are preferably substantive, cationic compounds which may be used as film-forming conditionerq having improved efficiency in cosmetic formulations, in particular in hair and skin care agent~.
The present invention also relates to cosmetic formulations which contain from 0.l to 35, in particular from 1 to 20, ~ by weight of one or more of the novel polymers as film-forming conditioners.
In the area of hair cosmetics, these products are components of conditioners, ~hampoos, hair setting compositions, hair rinses, waving compositions, bleaches and coloring agents and improve the wet combability of the hair and prevent electrostatic charging of dry hair.
In the case of damaged hair, the hair surface is smoothed and the strength increased (curative effect). Owing to their film-forming properties, the novel products give greater body to the hair.
Owing to the very good compatibility with anionic surfactants and anionic polymers, the novel polymers are particularly suitable as an active ingredient in condi-tioning shampoos, bath gels and similar formulations.
Novel polymers having slight cationic activity are compatible with carbomer polymers and are suitable for the preparation of conditioner gels.
Products having X value~ of from l00 to 350 or from 150 to 450 (mea~ured in respective 1% strength by weight and 0.l~ strength by weight aqueous solutions of the polymers at pH 7 and 25C) are preferably required for conditioners and hair setting compositions, while productq having K values of from 8 to 200 or from 8 to 250 (measured in respective 1~ strength by weight and 4~7~7~7 - ~2 - O.Z. 0050/ 25~2 0.1% strength by weight aqueous solutions of the polymers at pH 7 and 25C) are required for shampoos, hair rinses, bleaches and coloring agent~.
As additives for hair care preparation~, these S products impro~e their spreadlng and impart a smooth and supple feel to the skin. The quality of shaving prepara-tions and soaps is improved by the foam stabilization or the gliding effect of the novel product~ used. They impart a silky feel to the skin, which is retained even after rin~ing of ~.
Novel polymers prepared with a predominant amount of monomers (b) are particularly suitable as polymeric components in iodophores (iodine complexes for medical applications), as adhesives, for example in adhesive pens or a~ color transfer inhibitors, or example in detergents or in the textile industry. Novel polymers prepared with a predominant amount of monomers (a) or mixtures of monomers (a) and (b) are also suitable as agents for preventing color transfer.
Iodophores prepared using novel polymers have an improved shelf life. When used as color transfer in-hibitors, an improvement is likewise obtained compared with the prior art.
The novel polymers may also be used as stabi-lizers for perfumes and perfume oils.
The pre~ent invention al~o relates to perfumes and perfume oils which contain from Ool to 50, in par-ticular from 1 to 10, % by weight of one or more novel polymers as stabilizer~.
The novel polymer~ are also suitable as conduc-tivity resins, as flocculants and as assistants in oil produ~tion.
A further advantage of the novel polymers is their substantial biodegradability or capability of being eliminated from the wastewaters of treatment plants.
Lastiy, the products are based on renewable raw materials in order further to improve ecological acceptance while . . ~.

.

2~7~7~7 - 23 - o.Z. 0050/425~2 at the same time a similar or even improved property profile compared with purely synthetic cosmetic products.
The novel polymers having an predominant amount of monomers (b) are further}nore suitable for all applications in which PVP is used.
EXAMPI,ES
In the Example~ which follow, percentages are by weight, unless stated otherwise.
Preparation and properties of the polymer~
The K values of the polymers were determined according to H. Fikentscher, Cellulosechemie, 13 (1932), 58-64 and 71-74, K being k x 103. The mea~urements were carried out in 1~ strength of 0.1% stxength aqueous solutions of the polymers at 25C and at a pH of 7.
lS The D~ values of the starches or their deriva-tives are dextrose equivalents. They were determined by the Luff-Schoorl method (cf. G. Tegge, Starke und Starkederivate, Behr~s Verlag, ~amburg 1984, page 305).
EX~MPLE 1 A mixture of 180 g of vinylimidazole quaternized with dimethyl sulfate, 80 g of vinylpyrrolidone and 460 ml of water formed feed 1. Feed 2 was prepared from feed 1, 44 g of 2,2'-azobis-(2-amidinopropane) dihydrochloride and 100 ml of water. 80 g of sucrose, 300 ml of water, 200 ml of feed 1 and 35 ml of feed 2 were heated to 60C, while stirrlng, in a 2 1 flask equipped with a stirrer, a heating mean~, a reflux condenser, a thermometer, metering apparatuses and ni~rogen inlet and outlet apparatuses. After the in-tended temperature had been reached/ the remainder of feed 1 was metered in over 5 hours and the remainder of feed 2 in the course of 6 hour~ at a constant temperature of 60C. Thereafter, stirring was continued for a further 2 hours at thi~ temperature. A clear, highly viscou~
polymer solution having a solids content of 20.4% was obtained. The K value (0.1% strength in water) was 238.5.

2~7~7~7 - 2~ - O.Z. 0050/42582 Example 1 was repeatecl, except that, instead of sucrose, the same amount of maltodextrin having a DE
value of from 11 to 14 was used. A clear, colorless, highly viscous solution having a solids content of 20.2%
was obtained. The K value (0.1% strength in water) was 257.5. The residual vinylpyrr.olidone content was below the limit of detection labout 10 ppm).

Example 1 was repeated, except that 1.45 g of potassium peroxydi~ulfate were used instead of 2,2' azobis-(2-amidinopropane) dihydrochloride, and polymeriz-ation was initiated at 90C. A clear, viscous solution having a solids content of 19.8% was obtained. The K
value (0.1% strength in water) wa~ 162.3, EXAMP~E 4 Example 2 was repeated, except that, instead of ~,2'-azobis-(2-amidinopropane) dihydrochloride, a mixture of 1.2 g of H2O2 (30% strength in water), 0.05 g of FeCl3 6 H20 and 100 ml of water were used as feed 2, and polymerization waq effected at 80C. A clear, viscous solution having a ~olids content of 20.1~ was obtained.
The K value (0.1% strength in water) was 168.4.

Feed 1 con~isted of a mixture of 515 g of vinyl-imidazole quaternized with methyl chloride, 600 ml of water and 50 g of isopropanolO Feed 2 was prepared from 4.6 g of tert-butyl 2-ethylhexanoate and 157 g of iso-propanol. 180 g of potato starch, 180 ml of water, 120 ml of fe,ed 1 and 20 ml of feed 2 were initially taken in a 2 l flask equipped with a heating means, a stirrer, a reflux condenser, nitrogen inlet and outlet and meter-ing means and were gently refluxed (at about 85C).
Thereafter, with constant gentle boiling, th~ remainder of feed 1 was metered in over 6 hours and the remainder ~74~
- 25 - o.Z. 0050/42582 of fePd 2 in the course of 8 hours, after which the mixture was kept at the boil for a further hour. The isopropanol wa~ then expelled by passing in steam. A
clear, viscous polymer solution was obtained. The K
value of the polymer ~as 55.2 (1% strength in water).

Feed 1 consisted of a mixture of 203 g o~ vinyl-imidazole quatexnized with dimethyl sulfate, 203 g of vinylpyrrolidone and 220 g of water. A solution of 101.4 g of 2,2'-azobis-(2-amidinopropane) hydrochloride in 75 g of water wa~ used as feed 2. 200 g of water, 106 ml of feed 1, 5 ml of feed 2 and 100 g of maltodextrin having a DE value of 11 to 14 were initially taken in a 2 1 glass vessel equipped with a stirrer~ a heating means, a reflux condenser, nitrogen inlet and outlet and metering means and were heated to 65C. Thereafter, at this temperature, the remainder of feed 1 was metered in over 5 hours and the remainder of feed 2 in the course of 7 hours and ~tirring was continued for a further hour.
A clear, viscous polymer solution was obtained. The K
value of the polymers wa~ 125.4 tl~ strength in watsr).
The residual vinylpyrrolidone content was below the limit of detection (< 10 ppm) and the solids content after dilution with 800 ml of water was 28.0%.

Example 6 was repeated, except that the same amount of dextrin (white) was used in~tead of malto-dextrin. The ~olids content wa~ 48.6% and the K value (1% strength in water) was 124.1.
30EXAMP~E 8 Feed 1 consisted of a mixture of 203 g of vinyl-imidazole quaternized with methyl chloride, 200 g of vinylpyrrolidone, 240 g of water and 1 g of 2-mercapto-ethanol. A solution of 2.4 g of 2,2'-azobis-(2-amidino-35propane) dihydrochloride in 75 g of water wa~ used as feed 2. 200 g of water, 100 ml of feed 1, 10 ml of feed ~0747~rJ
- 26 - O.~. 0050/42582 2 and 100 g of 82.4% strength potato starch were initial-ly taken in a 2 l glass vessel equipped with a stirrer, a heating mean~, a reflux condenser, gas inlet and outlet and metering means and were heated to 60C. Thereafter, at this temperature, the remainder of feed 1 wa~ metered in over 5 hours and the remainder of feed 2 in the course of 7 hours, and stirring was continued for a further hour. A clear, viscous polymer solution having a solids content of 48.3% was obtained. The K value (1% strength in water) wa~ 76.3.
EXAMPL~ 9 Example 8 was repeated, except that the Yame amount of glucose was used instead of potato starch. A
clear, viscou~ polymer ~olution having a solid~ content of 49.9% and a K value (1% strength in water) of 72.1 was obtained.

Feed 1 consisted of a mixture of 153 g of Jinylimidazole quaternized with methyl chloride, 150 g of vinylpyrrolidone, 150 g of glucose and 350 g of water.
A solution of 2.0 g of tert-butyl perneodecanoate in 30 g of ethanol was used as feed 2. 400 g of water, 200 ml of feed 1 and 10 ml of feed 2 were initially taken in a 2 l vessel equipped with a stirrer, a heating mean~, a reflux condenser, gas inlet and outlet and metering means and were heated to 55C. Thereafter, at this temperature, the remainder of fPed 1 was metered in over 5 hours and the remainder of feed 2 in the course of 7 hours, and stirring was continued for a further hour. A
clear, viscous polymer solution having a solid~ content of 36.1% wa~ obtained. The K value was 118.3 (1%
strength in water).

Example 10 waY repeated, except that the same amount of dl-tert butyl peroxide was used instead of tert-butyl plerneodecanoate. Polymerization wa9 carried ~07~7~7 - 27 - O.z. 0050/42582 out at 2.2 bar and 125C in a 2 1 pressure vessel, and a yellow, clear, viscous solution having a solids content of 37.4~ was obtained. The K ~Jalue was 92 . 4 ( 1% strength in water).
EXAMPLE' 12 Feed 1 consisted of a mixture of 120. 0 g of vinylimidazole quaternized with methyl chloride and 400 ml of water. A solution oi- 1.84 g of 2,2'-azobis-(2-amidinopropan~) dihydrochloricle and 100 ml of water was used as feed 2. 120 g of sucrose, 300 ml of water, 200 ml of feed 1 and 35 ml of feed 2 were initially taken in a 2 1 flask equipped with a stirrer, a heating means, a reflux condenser, gas inlet and outlet and metering means and were heated to 65C. Thereafker, at this temperature, the remainder of feed 1 was metered in over 5 hours and the remainder of feed 2 in the course of 6 hours, and stirring was continued for a further three hours. A yellow, clear, viscous polymer solution having a solids content of 20.2% was obtained. The K value of the resulting solution was 88.7~ (1% strength in water).

Feed 1 consisted of a mixture of 80 g of vinyl-imidazole quaternized with dimethyl sulfate, 80 g of vinylpyrrolidone and 560 g of water. A solution of 1.44 g of 2,2'-azobis (2-amidinopropane) dihydrochloride and 100 ml of water was used as feed 2. 80 q of sucrose, 250 ml of water, 200 ml of feed 1 and 35 ml of feed 2 were initially taken i~ a 2 1 flask equipped with a stirrer, a heating means, a reflux condenser, gas inlet and outlet and metering means and were heated to 60C. At this temperature, the remainder of feed 1 was metered in over 5 hours and the rem~inder o feed 2 in the course of 6 hours, and stirring was continued for a further two hours. A cleax, vi8cous polymer solution having a solids content of 20.6% was obtained. The K value of the resulting solution was 186.0 (0.1% strength in water).

2~747~7 - 28 - O.Z. 0050/42582 Feed 1 conslsted of a mixture which corresponded to that of Example 13. A solution of 1.44 g of 2,2'-a~obis-(2-amidinopropane) dihydrochloride in 100 ml of water was likewise used as feed 2. 80 g of sucrose, 200 ml of water, 200 ml of feed 1 and 35 ml of feed 2 were initially taken in a 2 l flask equipped with a stirrer, a heating means, a reflux condenser, gas inlet and outlet and metering means and were heated to 60C. At this temperature, the remainder of feed 1 wa~ metered in oYer 5 hours and the remainder of feed 2 in the course of 6 hours. After the addition of 100 ml o~ water, a clear/
colorless, highly viscous polymer solution having a solids content of 19.6~ was obtained. The K value of the resulting solution was 262.9 (0.1% strength in water).

Feed 1 consisted of a mixture of 133 g of vinyl-pyrrolidone, 51.5 g of dimethylaminopropylmethacrylamide quaternized with diethyl sulfate and 325 ml of water.
Feed 2 consisted of 0.44 g of 2,2'-azobis-(2-amidino-propane) dihydrochloride and 25 g of water. 80 g of sucrose, 390 ml of water, 165 ml of feed 1 and 80 ml of feed 2 were initially taken in a 2 l glass flask equipped with a ~tirrer, a heating means, a re~lux conden~er, gas inlet and outlet and a metering mean~ and were heated to 65C. At thi~ temperature, the remainder of feed 1 was metered in over 4 hours and the remainder of feed 2 in the course of 6 hours, and stirring was continued for a further two hours. A clear, viscous polymer solution having a solids content of 25.0% was obtained. The K
value of the resulting solution was 223.3 (0.1% strength in water).

Example 15 was repeated, except that the same amount of maltodextrin having a DE value (according to Luff-Schoorl) of from 11 to 14 was used in tead of sucro~e. A virtually clear, highly viscous polymer 2~7~7~7 - 29 - O~Z. 0050/42582 solution havlng a solids content of 25.6% was obtained.
The K value of the resulting solution was 119.3 (1%
strength in water).
E XA~PLE 17 Feed 1 consisted of a mixture of 180 g of vinyl-imidazole and 3~5 g of water. A ~olution of 1.0 g of 2,2'-azobis-(2-amidinopropane) dihydrochloride in 100 ml of water was used as feed 2. 90 g o~ ~ucrose, 390 ml of water, 170 ml of feed 1 and 35 ml of feed 2 were initial-ly taken in a 2 l flask equipped with a reflux condenser, a stirrer, a thermometer, a heating means, gas inlet and outlet and a metering meanR and were heated to 60C. At this temperature, the remainder of feed 1 was metered in over 5 hours and the remainder of feed 2 in the course of 7 hours, and stirring wa~ continued for a further 4 hours at 60C. A yellow, clear, viscous solution having a solids content of 24.9% was obtained. The K value of the resulting solution was 83.4 (1% strength in water).

Example 17 was repeated, except that enzymatical-ly degraded potato starch having a DE value of from 37.5 to 40.5 (according to Luff-Schoorl) was used instead of sucrose. A clear~ yellow, viscous polymer solution having a solids content of 25.1~ was obtained. The K
value of the resulting solution was ~9.5 (1% strength in water).

Feed 1 consisted of a mixture o~ 120 g of dimethylaminoethyl methacrylate and 560 g of water. A
solution of 1.44 g of 2,2'-azobis-(2-amidinopropane) dihydrochloride in 100 ml of water wa~ used as feed 2.
120 g of sucrose, 300 ml of water, 200 ml of feed 1 and 35 ml of feed 2 were initially taken in a 2 l flask equipped with a reflux condenser, a stirrer r a ther-mometer, a heating means, gas inlet and outlet and metering means and were heated to 60C. At this tempera-ture, the remainder of feed 1 was metered in over 5 hours , . , 2~7~7'~7 - 30 ~ O.Z. 0050/42582 and the remainder of feed 2 in the course of 6 hours, and stirring was continued for 2 hours at 60C. A clear, highly viscous, partially crosslinked polymer gel having a solids content of 19.6% was obtained. The K value 5could not be determined owing to the crosslinking.

Example 19 was repeat:ed, except that the same 2~mount of dimethylaminopropylmethacrylamide was used instead of dimethylaminoethyl methacrylate. A clear, 10viscous polymer solution having a solids content of 19.4%
was obtained. The K value of the resulting solution was 241.3 (0.1% strength in water).

Feed 1 consisted of a mixture of 80 g of 15dimethylaminoethyl methacrylate, 80 g of vinylpyrrolidone and 560 g of water. A solution of 1.44 g of 2,2'-azo~is-(2-amidinopropane) dihydrochloride in 100 ml of water was used as feed 2. 80 g of sucrose, 300 ml of water, 200 ml of feed 1 and 35 ml of feed 2 were initially taken in a 202 1 glass vessel equipped with a reflux condenser, a stirrer, a thermometer, a heating, gas inlet and outlet and metering mean~ and were heated to 60C. At this temperature, the remainder of feed l was metered in over 5 hours and the remainder of feed 2 in the course of 6 25hours, and stirring was continued for 2 hour~ at 60C.
A clear, colorless, partially crosslinked polymer gel having a solids content of 20.3% was obtained~ The R
value or the relative viscosity could not be determined owing to the crosslinking.

Feed 1 consisted of a mixture of 120 g of dimethylaminopropylmethacrylamide quaterni~ed with diethyl su]fate and 560 g of w~ter. A solution of 1.44 g of 2,2'-azobi~ (2-amidinopropane~ dihydrochloride 35in 100 ml of water was u~ed as feed 2. 120 g of sucrose, 300 ml of water, 200 ml of feed 1 and 3S ml of feed 2 were initially taken in a 2 l glass vessel equipped with 2~7~7~

- 31 - O.Z. 0050/425~2 a reflux condenser, a stirrer, a thermometer, a heatlng, gas inlet and outlet and a metering means and were heated to 60C. At this temperature, the remainder of feed 1 was metered in over 5 hours and the remainder of feed 2 in the course of 6 hours, and stirring wa~ continued for 2 hours at 60C. A clear, highly viscous polymer solution having a solids content of 19.8% was obtained. The X
value was 101.0 (~.1% strength in water).

Example 20 was repeated, except that a mixture of ~0 g of dimethylaminopropylmethacrylamide and. 23 yrrolidone was used instead of 120 g of dimethylaminopropylmethacrylamide. A highly viscous polymer solution having a solids content of 21.5% and a K value of 280.6 (0.1% ~trength in water) was obtained.

Feed 1 consisted of a mixture of 80 g of vinyl-imidazole quaternized with methyl chloride, 80 g of vinylpyrrolidone and 560 ml of water. A mixture of 1.44 g of 2,2' azobis-[2-~2-imidazolin-2-yl)-propane]
dihydrochloride in 100 ml of water was used as feed 2.
80 g of hydroxypro~ylcellulose, 300 ml of water, 200 ml of feed l and 35 ml of feed ~ were initially tak0n in a 2 l flask equipped with a reflux condenser, a stirrer, a thermometer, a heating, gas inlet and outlet and metering means and were heated to 45C. At this temperature, the remainder of feed 1 was metered in over 5 hours and the remainder of feed 2 in the course of 6 hours, and stirr-ing was continued for 2 hours at 60C. A slightly turbid, viscous polymer ~olution having a solids content of 21.4%
was obtained. The K value of the resulting solution was 204.0 (0.1~ strength in water).

Feed 1 consi~ted of a mixture of 80 g of vinyl-imidazole quaternized with methyl chloride, 80 g of vinylpyrrolidone and 560 ml of water. A mixture of 1.4 g of 2,2'-azobis-(2-amidinopropane) dihydrochloride 2~7~7~7 - 32 - O.Z. 0050/42582 in 100 ml of wa-ter was used as feed 2~ 20 g of ~odium carboxymethylcellulose, 300 g of water, 200 ml of feed 1 and 35 ml of feed 2 were initially taken in a 2 l flask equipped with a reflux condenser, a stirrer, heating, gas inlet and outlet and metering means and wer~ heated to 65C. At this temperature, the remainder of feed 1 was metered in over 4 hours and t:he remainder of feed 2 in the course of 6 hour~, and stirring wa~ continued for 2 hours. A slightly turbid, viscous polymer solution having a solids content of 20.3% was obtained. The K
value of the resulting solution was 199.8 (0.1% strength in water).

Feed 1 consisted of a mixture of 96 g of vinyl-imidazole quaternized with methyl chloride, 384 g of vinylpyrrolidone, 216 ml of water and 0.96 g of mercapto-ethanol. A mixture of 1.68 g of 2,2'-azobis-(2-amidino-propane) dihydrochloride in 78 ml of water was used as feed 2. 30 g of maltodextrin having a DE value of from 11 to 14 ~according to Luff-Schoorl), 60 ml of feed 1, 6 ml of feed 2 and 420 ml of water were initially taken in a 2 l flask equipped with a reflux condenser, a stirrer, a thermometer, heating means, gas inlet and outlet means and were heated to 65C. At thi3 tempera-ture, the remainder of feed 1 was metered in over 4 hours and the remainder of feed 2 in the course of 6 hours, and stirring was continued for 2 hours. A clear, viscous polymer solution having a solids content of 44.6% was obtained. The K value of the resulting solution was 69.4 (0.1% strength in water)O

Feed 1 consisted of a mixture of 200 g of di-methyldiallylammonium chloride and 300 g of water.
2.9 g of 2,2'-azobis-(2-amidinopropane) dihydrochloride in lO0 ml of water was used as feed 2. 100 g of sucrose, 150 ml of feed 1, 35 ml of feed 2 and 200 ml of water were initially taken in a 2 l glas~ vessel equipped with 2~7~7~7 _ 33 - o.z. 0050/42582 a reflux condenser, a stirrer, a thermometer, a heating rneans, gas inlet and outlet means and were heated to 65C.
At this temperature, the remai.~der of feed 1 was metered in over 6 hours and the remainder of feed 2 in the course of 8 hours, and stirring was continued for 2 hours. A
yellowish, viscous polymer solution having a solids content of 27.8% was obtainled. The K value of the resulting polymer solution was 42.1 (O.1% strength in water).

Example 27 was repeated, except that the same amount of potato starch was used instead of sucrose. A
yellow~ viscous solution having a ~olids content of 27.9~
was obtained. The K value of the resulting polymer solution was 47.9 (0.1% strength in water).

This Example corresponds to Example 13 from reference (1). A clear, viscous polymer solution having a solids content of 39.8% (0.1% strength in water) was obtained.

F~ed 1 consisted of a mixture of 203 g of vinyl imidazole quaternized with methyl chloride, 200 g of vinylpyrrolidone and 240 g of water. ~ solution of 2.4 g of 2,2'-azobis-(2-amidinopropan~) dihydrochloride in 75 g of water was used as feed 2. 200 g of water, 100 ml of feed 1 and 10 ml of feed 2 were initially taken in a 2 l glass ve~sel equipped ~ith a stirrer, heating mean~, a reflux condenser, ga~ inlet and outlet and metering means and were heated to 60C. Thereafter, at this temperature, the remainder of feed 1 was metered in over 5 hours and the remainder of feed 2 in the course of 7 hours, and stirring was continued fox a further hour. After dilution with 700 ml of water, a clear, viscous polymer solution having a solids content of 24.8%
was obtained. The K value of ths re3ulting polymer 2~7~7~7 - 34 - o.z. 0050/425a2 solution was 124.2 (0.1% strength in water).

Example 6 was repeatecl, except that maltodextrin was omitted~ A clear, viscous polymer solution having a solids content of 23.2% was obtained. The K value of the resulting solution was 127.3 ~0.1% strength in water).

Example 22 was repeated, except that all the sucrose, 360 ml of water from feed 1 and 120 ml of water from the initially taken mixture were omitted. A highly ~iscous polymer solution having a solids content of 20.3%
and a K value of 291.3 (0.1% strength in wa~er) was obtained.

This Example corresponds to Example 2 from referenc~ (3). A highly viscous polymer solution having a solids content of 20.2% was obtained. The K value was 299.7 (0.1~ strength in water).

~his Example corresponds to Example 6 from reference (2). A yellowi~h, viscous polymer solution having a ~olids co~tent of 21.2% wa~ obtained. The K
value was 286.3 (0.1~ strength in water).
Mixtures: Examples 35 to 58 A pol~mer solution, prepared according to Example 29, was mixed with sucrose in difference ratios.
A solution according to Example 31 w~s likewi~e mixed with sucrose.

2 ~ 7 - 35 - O~Z. 0050/42582 Example No. 35 3637 3: 39 40 Weight rati.o2:1 1:11:2 2:1 1:1 1:2 Polymer/Sucrose . _ .
Solid~ conte~t [~] 19.9 19.719.139.4 39.2 35.5 . . _ 0 K value (0.1~254.5 243.8 238.2161.3149.7 137.1 strength in H2O) _ Polymer from Ex. 29 29 29 31 31 31 Examples 35 to 40 were each xepeated, except that the same amount of maltodextrin having a DE value (according to Luff-Schoorl) of from 11 to 14 was used instead of sucrose.
TA~LE 2 Exampl~ No. 41 4243 44 45 46 Weight ratio 2:1 1:11:2 2:1 1:1 1:2 Polymer/Maltodextrin . _ solid~ content l%] 19.2 19.619.338.9 38.3 38.8 K value (0.1~257.2 244.2 232.0163.4 151.7 134.3 strength in H2O) _ . . __ .
Polymer from EX o 29 29 29 31 31 31 EXAM*LES 47 TO 49 A polymer according to Example 33 was mixed with different amounts of ~ucrose.

20~7~7 - 36 - O.Z. 0050/~2582 -TABI.E 3 Example No. 47 48 49 . __ Weight ratio 2:1 1:1 1:2 Polymer/sucrose . . ....
solids content [~] 19.3 19.7 20.7 _ R value (0.1% 288.3 278.4270.9 -qtr~ngth in H2O) A polymer according to Example 33 wa~ mixed with different amount3 of maltodextrin having a DE value (according to Luff-Schoorl) of from 11 to 14.

Example No. 50 51 52 Weight ratio 2:1 1:1 1:2 Polymer/Maltodex'crin solidq content [%] 20.5 21.8 19.0 _ _ X value ~0.1~289.3 276.4 264.3 ~trength in ~2) A polymer according to ~xample 34 was mixed with different amounts of sucro~e.

_ _ .
Example No . 5 3 5 4 5 5 Weight ratio 2:1 1:1 1:2 Po-ly~er/sucro~e Solids content l%] 20.7 20.0 19.6 R value ( O . 1~6 266 . 3 254 . 2 251. 0 qtrength in ~2 ~

A polymer according to Example 34 was mixed with different amounts of maltodextrin having a DE value (according to Luff-Schoorl) of from 11 to 14.

::

~7~7~7 - 37 - O.Z. 0050/42582 ~ABLE 6 Exalllple No. 55 = 58 weight ratio 2:1 1:1 1:2 polymer/Maltodextrin ..
Solid~ content [%] 20.0 19.0 21.2 R value (0.1% 269.4 256.0 253.2 strength in H2O) _ In Table 7, the properties of the novel polymer solutions according to Example~ 1 to 28 are compared with those of the formulations prepared for comparison accord--ing to Examples 29 to 58.
The properties of water absorption, compatibility with anionic surfactants, odor and color were compared.

Example Water Compatibility2) with Color3) Odor4) absorp- anionic ~urfactants in according after NTU to Gardner 7 day~

_ . ... ~_ 1 27.7 1.61 (clear) 2-3 30 2 26,0 1.70 (clear) 2 3 27.9 1.90 (clear) 2 2-3 4 28.3 2.0 (clear) 2 2-3 _ __ 26.3 262.5 (very turbid) 2-3 3-4 6 23.0 1.85 (clear) 2 7 25.9 2.5 (clear) 2 2 8 26.6 2.3 ~clear) 2-3 2 . . . .... ... ...
9 31.7 2.05 (clear) 2 2-3 29.3 2.1 (clear) 2 11 28.9 2.3 (clear) 2 3-4 12 30.:L 253.5 (vary turbid) 2-3 ~7~7l~7 - 38 - O.Z. 0050/42582 Example Water Compatibility2) with ¦eolor3) ab~orp- anionic surfactant3 in according after NNTU to Gardner 7 days . _ 13 25.0 2.4(elear) 2 1-2 _ _ . .
14 24.7 2.3 (elear) ~ _ . 2 26.7 1.81 (clear) 1-2 1-2 16 24.6 1.86 (elear) 2 __ _ 17 27.8 2.35 (elear) 2-3 3-4 18 30.3 2.4 (clear) 2-3 3 _ _ _ 19 25.1 _ 2-3 2-3 24.8 2.9 ~almost elear) 1 1-2 ~5 21 25.7 _ 2 2 .
22 29.8 270.3 (very turbid) 1-2 23 23.5 1.9 (clear) 1-2 1-2 24 33.3 3.5 (almo~t elear) 2-3 2 26.2 1.9 (clear~ 2 2-3 26 25.0 1.05 (elear) 1~2 1-2 27 29.3 _ _ 2-3 ~

28 28.9 _ 2-3 _ 2 29 45.7 8.0 (blui3h) 6-7 3-4 48.0 4.5 (almost elear) 3-4 3 31 37.1 2.2 (clear) 2-3 32 37.0 2.0 (clear) 2-3 33 33.4 2.3 ~elear) 2 34 38.5 11.2 (blui~h)2-3 3-4 _ . ..
34.9 5.9 (bluish) _ :
- ~ -.

' 2~7~7~7 - 39 - O.Z. 0050/42582 ~_ . . _ Example watar Compatibility2) wit:h Color3)odor4 absorp- anionic surfactant3 in according after NTU to Gardn~r 7[9d6]aYg _ _ 0 36 34.2 5.7 (bluish) 2 37 28.4 5.1 (bluish) 2 38 38.5 5.4 ~bluish) _ 2-3 39 33.2 5.9 (bluish) 2 _ . .
25.8 5.9 (bluish) 3 3 41 34.3 5.8 (bluish) 2-3 3 . .
42 26.3 5.4 (blui3h) 2-3 2 43 25.1 5.6 (bluish) 2 2 44 34.6 28 (turbid) 3 2-3 28.4 334 (very turbid) 3 2 46 25.3 380 (vary turbid) 2-3 2 47 38.0 8.3 (blui3h) 2 2 48 32.5 8.5 ~blui3h) 2 49 29.1 9.2 (bluish) 1-2 2 36.5 6.9 (bluish) 2-3 3 51 34.0 5.9 (bluish) 2-3 3 52 30.1 6.9 (blui~h) 2-3 53 35.1 8.2 (bluish) 2-3 2-3 _ _ _ 54 31.8 7.5 (bluish) 2 2-3 29.S 6.2 (blui~h) 2 1-2 56 34.fl ~.9 (blui3h) 2-3 2 57 32.0 8.9 (blui~h) 2 2 _ _ _ _ 58 30.2 7.3 (bluish) 1-2 1-2 - -2~747~7 - 40 - O.Z. 0050/42582 " Water a~sorption In a weiqhing bottle with a cover (50 mm diameter and 30 mm height), about 1 g of dry substance was dis-solved with a little ethanol or another solvent. After evaporation of the solvent, drying was effected for 5 hours at 105C in a standard drying oven. The bottle~
were placed in a de~iccator with concentrated sulfuric acid to allow them to cool. After the closed bottles had cooled, the exact film weight was determined by weight.
Thereafter, the weighing bott:Les were opened again and placed in a 10 liter desiccator containing about 1 liter of sulfuric acid (specific gravity 1.221), which gave a relative humidity of 75% in a closed space (20C). After 7 days, the bottles were closed and weighed, and the percentage moisture absorption was calculated on the basis of the weight increase.
Z) Compatibility with anionic surfactants 1 part by weight of polymer solution was mixed with 9 parts by weight of sodium laurylethersulfate (14%
by weight) and the mixture was thoroughly stirred.
Thereafter, the resulting solution was placed in a cell and was mea~ured using a laboratory turbidity met~r, ~atio/XR Turbidimeter from Hach Comp., ~oveland, U.S.A., Model 43900, at room temperature. The turbidity was measured in nephelometric turbidity units (abbreviated to NTU). The higher the value, the more turbid is the measured liqllid or solution.
3) Color The Gardner color number according to DIN-ISO
4630 (November 1982) or ASTMD 1544-80 was determined.
4 ~ Odor The ~ollowing classification wa~ used:
l = Odorles3 2 = Slight natural odor 3 = Slight odor of imidazole or amine 4 = Odor of imidazole or amine 5 = Stronq odor of imidazole or amine 2~7~7~7 - 41 - o.z. 0050/~2582 Use Examples Formulations ~or hair conditioners:
Examples 59 to 62 EXAMPLE 59 ~or comparison) 2.0% of the polymer from Example 29 (based on solid substance) 0.5% of cetylhydroxyethyldi1nethylammonium dihydrogen phosphate l.Q% of a copolymer of 60% of vinylpyrrolidone and 40~ of vinyl a~etate C.1% of a commercial perfume 0.3~ of a commercial solubilizer 0.2% of a commercial preservative bassd on 2-methyl-4-i~othiazolin-3-one 85.9~ of distilled water 10.0% of propane/butane (25%/75%) The active ingredient was dissolved to give a clear solution. The setting effect on the hair was good but the resulting foam was creamy.

The composition corresponded to the formulation of Example 59, except that, instead of the polymer from Example 29, the same amount of polymer from Example 10 was used.
The active ingredient was dissolved to give a clear solution, the setting effect on the hair was good and a good, dry foam was obtai~ed.

The composition corresponded to the formulation of Example 59, except that, instead of the polymer from Example 29, the same amount of polymer from Example 14 was used.
The active ingredient was dissolved to give a clear solution, the setting ef~ect on the hair was very good and a good, dry foam was obtained.
EXA~P~E 62 The composition corresponded to the formulation ,, :

207~7l~ ~

- 42 - O.Z. 0050/42582 of Example 59, except that, instead of 2.0% of the polymer from Example 29, 2.5% of the polymer from Example 15 and coxrespondingly less dlstilled water we~e u~ed.
The active ingredient: was dissolved to give a clear solution, the qetting effect on the hair was very good and a good, dry foam was obtained.
Formulations for blow drying lotions as conditioners and setting compositions:
Examples 63 to 66 EXAMPLE 63 (for comparison) 1.0% of the polymer from Example 29 0.5% of cetylhydroxyethyldimethylammonium dihydrogen phosphate 1.0% o a copolymer of 60% of vinylpyrrolidone and 40% of vinyl acetate 0.1% o a commercial perfume O.3~ of a commercial solubilizer 20.0% of ethanol 77.1~ of distilled water The setting effect on the hair was good. The active ingredient had dissolved to give a clear solution.

The composition corresponded to the formulation of Example 63, except that, instead of the polymer from Example 29, the same amount of the polymer from Example 10 was used.
The setting effect on the hair was good to very good. The active ingredient had dissolved to give a clear solution.

The composition corresponded to the formulation of Example 63, except that, instead of the polymer from Example 29, the same amount of the polymer from Example 14 was used.
The setting effect on the hair was very good.
The active ingredient had dissolved to give a clear solution.

' ~: J
'~
~ ' . ;

2~ 74 7l~ ~
- ~3 - o.z. 0050/42582 The composition corre~ponded to the formulation of Example 63, except that, instead of the polymer from Example 29, the ~ame amount of the polymer from Example 15 was used.
The setting effect on the hair was very good.
The active ingredient had dissolved to give a clear solution.
Foam effect:

In a 1 1 beaker (high form), 1.0 g (based on the solid substance) of the particular polymer was added (except in the case of the blank sample) to a solution of 0.5 g of sodium lauryletherYulfate in 600 ml of water and stirring was carried out at 25C with a blade stirrer (diameter 5 cm) for 1 minute at 1400 rpm. 30 second~
after the stirrer had been switched off, the height of the foam was read (first value). Stirring was then continued for a further 3 minutes. Once again, 30 seconds after the stirrer had been switched off, the height of the foam wa again read (second value).
The results are shown in Table a.

Foam effect Polymer from Height of foam [cm]
Example 1st value 2nd value - (Blank sample) 2.6 3.8 . ..
2g (for comparison) 1.6 3~2 _ _ 1.2 3.6 14 1.8 3.
__ _ .
2.6 3~5 40The water phase was clear in all tests.
Formulation for hair shampoos: Example 68 2~74 7l17 - 44 - O.Z. 0050/42582 40.0~ of sodium laurylethersulfate 10.0% of cocamidopropylbetaine 10.0% of hydrolyzed animal pr~teins 5.0% of the polymer from Example 10 or 14 1.0% of a commercial solubilizer 0.05% of a commercial W Rtabilizer based on a benzo-phenone derivative O.1% of a c~immercial preservative based on 2 methyl-4-isothiazolin~3-one 0.8% of sodium chloride ~ater to 100~
In the formulation tested, both polymer~ ex-hibited good behavior as shampoo.
Formulation for hair packs: Example 69 3.0% of commercial emulsifiers 4.0~ of cetylstearyl alcohol 2.0% of cetearyl octanoate 0.1% of silicone oil 5.0~ of the polymer from Example 10, 14 or 15 2.0~ of panthenol 2.5% of propylene glycol O.1% of a commercial preservative water to 100%
All three polymers could be used in emulsion.
After storage for 6 weeks at 6C, 25C and also at 43C, in no case wa~ any change found in the formulation.
~XAMPLE 70 760 g of a starch saccharification produ~t having a DE value of from 17 to 19.9 were dissolved in 570 g of water, a~ter which 190 g of N-vinylpyrrolidone and 2 g of a 75% strength by weight solution of tert-butyl pexpiva-late in hyclrocarbon~ (Luperox 11 from Pennwalt) were added. Aft~r. the mixture had been heated to 75C, 570 g of N-vinylpyrrolidone were added dropwise in the course of two hours and simultaneously 10 g of a 7S% strength tert-butyl perpivalate solution in 100 g of ethanol w~re added dropwise in the cour~e of three houxs. After the 2~7~7'17 - 45 - o.z. 0050/4~582 ad~ition of a ~urther 10 g of the tert-butyl perpivalate solution in 100 g of ethanol, the temperature was then increased to 90C and ~tirring was carried out for a further two hours. After the ethanol had been separated o~f by st~am distillation, the mixture was diluted with 500 g of water. The solids content of the ~lightly yellow, turbid solution was 4t).6% and the K value of the polymer was 46 (1% strength in water).
Preparation of the iodine complex:
285 g of the polymer 6~01ution thus obtained were diluted with 468 g of water, after which 1.3 g of formic acid and 28 g of iodine were added. Stirring wa~ then ca~ried out for one hour at room temperature and twenty hours at 70C. An iodine compl~x solution with a solid~
content o~ 17.~ and an available iodine content (titratable with thio~ulate solution) of 11.7% tbased on solids) wa~ obtained. The conte~t of uncomplexed iodin (determined by dialy~is) in a solution diluted to an available iodine conten~ of 1% was only 0.0007%. The dilute solution had a long shelf lie. It lo~t only 2% o~
its content of available iodine after storage for 15 hour~ at 30C.
Use as a color transfer inhibitor Dye transfer from colored textile~ to white or pale textiles when they are washed together i5 a problem which has long been known and ha~ become increasingly important becau~e of the increased tr~nd towards washing everything together ~colored ~. To prevent tran~fer of the dye, the use of detergents having dye transfer inhibiting properties i~ recommended.
The patent literature describe~ detergents and cleaning ag~nt~ who~e dye tran~fer inhibiting a~tion is based on th~ addition of homo- or copolymers of N-vinyl-pyrrolidone (NVP) or of N-vinylimidazols (NVI) (German Laid-Open Applications DOS 2,232,353 and DOS 2,814,287).
The disadvantage of a polymer based on NVP is that it is not sufficiently effective against a ~umber of ~taining 2~747~7 - ~6 - O.Z. 0050/42582 dyes. Polymers based on NVI are more e~fective but tend to produce very unpleasant odors. These polymers have the common disadvantage that they are neither biodegradable nor capable of being removecl from the wastewater by sewage sludge absorption.
General remarks on the wash tests To test the efficien~y, white test fabric was washed together with dyed cott:on samples in a laundero-meter. The r~sulting dye transfer was measured photometrically. The depth of shade was in each determined from the reflectance values measured for the individual test fabrics, and the efficiency of the polymers can be derived from said depths. An efficiency of 100~ means that the test fabric retained its original depth, ie. it had not been stained. An efficency of 0%
was determined in the case of a test fabric which has the same depth as a test cloth which was washed without the addition of the dye transfer-inhibiting additive.
The textile samples were dyed with the following dyes:
Direct Black 51 (C.I. 27,720), Direct Blue 218 (C.I. 24,401), Direct Red 79 (C.I. 29,065), Direct Black 22 135,435), Direct ~lue 71 (C.I. 34,140) and Reactive ~lack 5 (C.I. 20,505).

Wa~hing conditions Washing apparatus Launderometer Wash cycles Temperature 60C
Washing time 30 min Water hardness 3 mmol Ca2+, Mg2~ (4:1) /1 Test fabric cotton Liquor ratio 50:1 Amount of liquor 250 ml Detergent concentration 7.0 g/l ~07~7~
- 47 - O.Z. 0050/42582 Detergent composition [%]
Zeolite A 20 Sodium carbonate 11 Linear dodecylbenzenesulfonate 5 Soap 1.3 Cl3/Cl5-oxo alcohol 7 ethylene oxide units 3.9 70:30 acrylic acid/maleic acid copolymer, 2.7 Na salt, MW = 70000 Na carboxymethylcellulose 0.4 Water 7.0 Polymer 1, 2 or 3 1.0 Sodium sulfate 100 Polymer 1 Polyvinylpyrrolidone, K value 30 (1% strength in H2O) standard polymer for comparison 5 Polymer 2 Synthesis according to the method stated in Example 72 Polymer 3 Synthesis according to the method stated in Example 71 Result Efficiency [~]
Polymer 1 ~olymer 2 Polymer 3 Direct Black 51 35 36 28 Direct Blue 218 38 42 100 Direct Red 79 83 86 87 Direct Black 22 81 87 ~1 Direct Blue 71 98 99 93 Reactive Black 5 17 13 - 46 The results show that pol~mers 2 and 3 prepared in the presence of saccharides (saccharide content 30 or 50%) not only achieve the effect of polyvinylpyrrolidone but even surpass it. Saccharides alone are ineffective.

Synthesis examples A m.ixture of 95 g of N-vinylimidazole, 3ao g of 2 ~ 7 ~ 7 !1 7 - 48 ~ o.Z. 0050/~2582 degraded starch (Luff-Schoorl DE value: 17-20) and 285 g of water was initially taken in a ~tirred apparatus with an attached reflux condenser and was heated to 85C in a stream of nitrogen with the addition of 1.1 g of tert-butyl peroxy-2-ethylhexanoate. After this temperature had been reached, ~eed 1 (285 g of N-vinylimidazole) waQ
added dropwise in the course of 2 hours and feed 2 ~5.1 g of tert-butyl peroxy-2-ethylhexanoate in 50 ml of ethanol) in the course of 3 hours. Thereafter, a solution of 5.7 g of tert-butyl peroxy-2-ethylhexanoate in 25 ml of ethanol was added and the reaction mixture was heated at 95C for 1 hour. After the end of the reaction, the mixture was cooled and was diluted with 300 ml of water.
A brownish, clear, viscous liquid which had no unpleasant odor was obtained. The K value (1~ strength in water) was 41.4.

A mixture of 50 g of N-vinylpyrrolidone, 120 g of sucrose and 280 ml of water was initially taken in a stirred apparatu~ with an attached reflux condenser and was heated to 60C in a stream of nitrogen with the addition of 1.20 g of 2,2'-azobis(2-amidinopropane) dihydrochloride. After this temperature had been reached, feed l (230 g of VP in 250 ml of water) waq metered in over 5 hour~ and feed 2 (2.20 g of 2,2'-azobis(2-amidino-propane) dihydrochloride in 70 ml o~ water) over 6 hours.
Polymerization was then continued for 2 hours at 60C. A
pale brown, clear, viscous liquid having a K value of 54 (0.1~ strength in water) was obtained.

Claims

1. A polymer of ethylenically unsaturated compounds which contain one or more covalently bonded nitrogen atoms in the molecule, polymerized in the presence of monosaccharides, oligosaccharides, poly saccharides or derivatives thereof, obtainable by polymerization, initiated by free radical initiators, in aqueous systems, of (A) monomers or monomer mixtures selected from the group consisting of (a) N-vinylimidazoles which may be substituted in the heterocyclic ring by not more than three C1-C12-alkyl radicals and may be present in the N-quaternized form or in salt form, (b) five-membered to eight-membered N-vinyllactams which may be substituted in the ring by not more than three C1-C12-alkyl radicals, (c) dialkylaminoalkyl acrylates or methacrylates where the dialkylaminoalkyl radical has a total of not more than 30 carbon atoms and which may be present in the N-quaternized form or in salt form, (d) N-(dialkylaminoalkyl)-acrylamides or -meth-acrylamides where the dialkylaminoalkyl radical has a total of not more than 30 carbon atoms and which may be present in the N-quaternized form or in salt form and (e) diallyl-C1-C12-alkylamines or salts thereof or diallyldi-(C1 C12-alkyl)-ammonium compounds, further comonomers (A) which may be present being (f) monoethylenically unsaturated C3-C10-carboxylic acids and alkali metal/ alkaline earth metal or ammonium salts thereof, (g) monoethylenically unsaturated C3 C10-carbox-ylates and (h) small amounts of compounds which contain two or more ethylenically unsaturated, non-- 50 - O.Z. 0050/42582 conjugated double bonds in the molecule, in the presence of (B) monosaccharides, oligosaccharides, polysaccharides, thermally or mechanically treated, oxidatively, hydrolytically or enzymatically degraded poly-saccharides, oxidized hydrolytically degraded or enzymatically degraded polysaccharides, chemically modified mono-, oligo- or polysaccharides or a mix-ture of the stated compounds (B) in a weight ratio (A) : (B) of (95 to 20) : (5 to 80).

2. A polymer as claimed in claim 1, in which either the compounds (a), (c), (d) or (e) alone or mixtures of from 5 to 95% by weight of a compound (b) and from 95 to 5% by weight of one or more of the monomers (a), (c), (d), (e), (f), (g) and (h) are used as monomers (A), (h) being employed in an amount of not more than 5% by weight, based on the total amount of all monomers (A).

3. A process for the preparation of a polymer of ethylenically unsaturated compounds which contain one or more covalently bonded nitrogen atoms in the molecule, polymerized in the presence of monosaccharides, oligo-saccharides, polysaccharides or derivatives thereof, wherein (A) monomers or monomer mixtures selected from the group consisting of (a) N-vinylimidazoles which may be substituted in the heterocyclic ring by not more than three C1-C12-alkyl radicals and may be present in the N-quaternized form or in salt form, (b) five-membered to eight-membered N-vinyllactams which may be substituted in the ring by not more than three C1-C12-alkyl radicals, (c) dialkylaminoalkyl acrylates or methacrylates where the dialkylaminoalkyl radical has a total of not more than 30 carbon atoms and which may be present in the N-quaternized form or in salt form, - 51 - O.Z. 0050/42582 d) N-(dialkylaminoalkyl)-acrylamides or -meth-acrylamides where the dialkylaminoalkyl radical has a total of not more than 30 carbon atoms and which may be present in the N-quaternized form or in salt form and (e) diallyl-C1-C12-alkylamines or salts thereof or diallyldi-(C1-C12-alkyl)-ammonium compounds, further comonomers (A) which may be present being (f) monoethylenically unsaturated C3-C10-carboxylic acids and alkali metal, alkaline earth metal or ammonium salts thereof, (g) monoethylenically unsaturated C3-C10-carbox-ylates and (h) small amounts of compounds containing two or more ethylenically unsaturated, nonconjugated double bonds in the molecule, are subjected to free radical polymerization in the presence of (B) monosaccharides, oligosaccharides, polysaccharides, thermally or mechanically treated, oxidatively, hydrolytically or enzymatically degraded poly-saccharides, oxidized hydrolytically degraded or enzymatically degraded polysaccharides, chemically modified mono-, oligo- or polysaccharides or a mixture of the stated compounds (B) in a weight ratio (A) : (B) of (95 to 20) : (5 to 80).

4. A method of using a polymer as claimed in claim 1 as a film-forming conditioner in cosmetic formulations.

5. A cosmetic formulation containing from 0.1 to 35%
by weight of one or more copolymers as claimed in claim 1 as film forming conditioners.

6. A method of using a polymer as claimed in claim 1 as a stabilizer for perfume and perfume oils.

7. A perfume or perfume oil containing from 0.1 to 15% by weight of one or more polymers as claimed in claim 1 or 2 as stabilizers.

8. A method of using a polymer as claimed in claim - 52 - O.Z. 0050/42582 1, prepared with predominant amounts of monomers b), in iodophore compositions or as adhesives or as color transfer inhibitors.

9. A method of using a polymer as claimed in claim 1, prepared with predominant amounts of monomers a) or a mixture of monomers a) and b), as color transfer inhibitors.