DE19533269A1 - Process for the preparation of polymers in an aqueous medium - Google Patents

Abstract

The invention relates to a method for the production of polymerisates from monomers insoluble in water and monomers optionally soluble in water by radical polymerisation of the monomers in water as the diluting agent, wherein the monomers insoluble in water are used in the form of complexes consisting of (a) cyclodextrins and/or compounds containing cyclodextrin structures, and (b) monomers which are insoluble in water or ethylenically unsaturated and soluble in water up to a maximum of 20 g/l at 20 DEG C, in the mol ratio (a):(b) of from 1:2 to 10:1, or the monomers are polymerised in the presence of up to 5 mol, in relation to 1 mol of the monomers (b), of cyclodextrins and/or compounds containing cyclodextrin structures. It also relates to the use of the polymerisates as sizing agents for the production of paper, as coating agents, as thickening agents for aqueous systems, as detergent additives and as thickening agents in cosmetic creams or lotions.

Description

The invention relates to a process for the production of polyme risks from water-insoluble monomers and possibly what water-soluble monomers by radical polymerization of the Mo nomers in a diluent.

The radical polymerization of monomers in aqueous solutions gene is of particular technical interest. requirement for However, a solution polymerization of the monomers is that the Also dissolve monomers in the solvent used. So For example, it is not possible to use non-polar monomers according to Art a solution polymerization to polymerize in water. Water soluble monomers, such as acrylic acid or maleic acid, are indu strictly according to the method of solution polymerization in water produced. The copolymerization of, for example, acrylic acid with water-insoluble monomers is therefore in an aqueous medium not possible.

According to the process of water-in-oil emulsion polymerization who which also free-radically polymerizes water-soluble monomers. However, this method fails even when larger quantities of water-insoluble comonomers incorporated into the copolymer should be because the water-soluble monomers in the aqueous Phase and the water-insoluble monomers in the oil phase polyme Rize so that there is virtually no copolymerization.

Also in the bulk polymerization of water-soluble and water insoluble monomers, it is necessary that the different Monomers are compatible with each other to form uniform polymers to get sate. This is very different for comonomers However, polarity is not guaranteed. Also with other buttocks Polymerization techniques such as precipitation polymerization is the Un Compatibility of water-insoluble monomers with the aqueous Media is often a major disadvantage.

It is also known from the prior art that cyclodextrins can serve as organic host molecules and are able to one or two guest molecules forming supramolecular To include structures, cf. W. Saenger, Angew. Chem. Int. Ed. Engl. 1980, 19, 344 and G. Wenz. Appl. Chem. Int. Ed. Engl. 1994, 33, 803-822. For example, there are crystalline complexes known from ethylene and cyclodextrin.  

From J. Macromol. Sci. Chem., A13, 87-109 (1979) are inclusion ver bindings of polymers known by radical polymeri sation of monomers in a β-cyclodextrin matrix in dimethyl formamide solution. The monomers are vinylidene called chloride, methyl acrylate, styrene and methacrylonitrile.

DE-A-40 09 621 combines quick-setting adhesives settlements based on α-cyanoacrylates known in α-cyan Acrylates at least partially soluble derivatives of cyclodextrins contain.

The present invention has for its object a Ver drive to the production of polymers from water-insoluble Monomers and optionally water-soluble monomers radical polymerization of the monomers in a dilution to provide funds.

The object is achieved according to the invention if the polymeri sation in water as a diluent and the water insoluble monomers in the form of complexes

• (a) Cyclodextrins and / or cyclodextrin structures containing Connections and
• (b) water-insoluble or at most up to 20 g / l at 20 ° C serially soluble ethylenically unsaturated monomers

in the molar ratio (a): (b) from 1: 2 to 10: 1 or the mono mer in the presence of up to 5 moles, based on 1 mole of the mono mer (b), on cyclodextrins and / or cyclodextrin structures holding compounds polymerized.

Cyclodextrins are those in the literature mentioned above consider described α-, β-, γ- and δ-cyclodextrins. They are, for example, by enzymatic breakdown of starch won and consist of 6 to 9 D-glucose units, which over an α-1,4-glycosidic bond are linked together. α-Cy clodextrin consists of 6 glucose molecules. Taking cyclodextrin compounds containing structures are said to be reaction products be understood by cyclodextrins with reactive compounds, e.g. B. reaction products of cyclodextrins with alkylene oxides such as Ethylene oxide, propylene oxide, butylene oxide or styrene oxide, conversion tion products of cyclodextrins with alkylating agents, e.g. B. C₁- to C₂₂ alkyl halides, e.g. B. methyl chloride, ethyl chloride, butyl chloride, ethyl bromide, butyl bromide, benzyl chloride, lauryl chloride, Stearyl chloride or behenyl chloride and dimethyl sulfate. A white tere modification of cyclodextrin is also possible through implementation  Chloroacetic acid possible. Derivatives of cyclodextrins, the Cyclo dextrin structures are also included by enzymatic Linkage with maltose oligomers available. Examples of Um Settlement products of the type specified above are dimethyl-β-cyclo dextrin, hydroxypropyl-β-cyclodextrin and sulfonatopropylhydroxy propyl-β-cyclodextrin. From the compounds of group (a) is preferably used α-cyclodextrin, β-cyclodextrin, γ-Cy clodextrin and / or 2, 6-dimethyl-β-cyclodextrin.

The compounds of group (b) include water-insoluble or at most up to 20 g / l ethylenically soluble in water at 20 ° C unsaturated monomers. Examples of such compounds are C₂- to C₄₀ alkyl esters of acrylic acid or C₁ to C₄₀ alkyl esters of Methacrylic acid, such as methyl methacrylate, ethyl acrylate, ethyl meth acrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, Is propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, pentyl acrylate, Pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyla crylate, n-heptyl methacrylate, n-octyl acrylate, n-octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, decyl acrylate, De cyl methacrylate, lauryl acrylate, lauryl methacrylate, palmityl acrylate, palmityl methacrylate, octadecyl acrylate, Qctadecylmetha crylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl acrylate and phenyl methacrylate.

Other monomers of group (b) are α-olefins with 2 to 30 C- Atoms and polyisobutylenes with 3 to 50, preferably 15 to 35 Isobutene units. Examples of α-olefins are ethylene, Propylene, n-butene, isobutene, pentene-1, cyclopentene, hexene-1, Cyclohexene, octene-1, diisobutylene (2,4,4-trimethyl-1-pentene against optionally in a mixture with 2,4,4-trimethyl-2-pentene), decene-1, Dodecen-1, Octadecen-1, C₁₂ / C₁₄-olefins, C₂₀ / C₂₄-olefins, styrene, α-methylstyrene, polypropylenes with terminal vinyl or vinyl Liden group with 3 to 100 propylene units, oligohexene or oli gooctadecen.

Another class of monomers of group (b) are N-alkyl sub substituted acrylamides and methacrylamides, such as N-tert-butylacry lamide, N-hexyl methacrylamide, N-octylacrylamide, N-nonyl methacryla mid, N-dodecyl methacrylamide, N-hexadecyl methacrylamide, N-metha crylamidocaproic acid, N-methacrylamidoundecanoic acid, N, N-dibutyla crylamide, N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylic amid.

Other monomers of group (b) are vinyl alkyl ethers with 1 to 40 Carbon atoms in the alkyl radical, for example methyl vinyl ether, Ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-Bu  tyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2- (diethyl amino) ethyl vinyl ether, 2- (di-n-butylamino) ethyl vinyl ether, Me thyl diglycol vinyl ether and the corresponding allyl ethers such as Allyl methyl ether, allyl ethyl ether, allyl n-propyl ether, allyl isobutyl ether and allyl-2-ethylhexyl ether. They are also suitable as compounds of group (b) the water-insoluble or sup at least up to 20 g / l water-soluble esters of maleic acid and Fumaric acid, which differs from monohydric alcohols with 1 to 22 Derive carbon atoms, for example maleic acid mono-n-bu tylester, maleic acid dibutyl ester, maleic acid monodecyl ester, Ma linseed acid didodecyl ester, maleic acid monooctadecyl ester and Ma linseic acid dioctadecyl ester. Vinyl esters from are also suitable saturated C₃ to C₄₀ carboxylic acids such as vinyl propionate, vinyl butyrate, vinyl valerate, vinyl 2-ethylhexanoate, vinyl decanoate, Vi nyl palmitate, vinyl stearate and vinyl laurate. Other monomers of Group (b) are methacrylonitrile, vinyl chloride, vinylidene chloride, Isoprene and butadiene.

The above-mentioned monomers of group (b) can be used alone or in Mixture for the preparation of the complexes or during the polymerization be used. Coming into consideration preferably as monomers (b) Mende compounds are C₂ to C₃₀ alkyl esters of acrylic acid, C₁- to C₃₀-alkyl esters of methacrylic acid, C₂- to C₃₀-α-olefins, C₁- to C₂₀ alkyl vinyl ether, styrene, butadiene, isoprene or their Mixtures. Particularly preferred monomers (b) are methyl meth acrylate, butyl acrylate, lauryl acrylate, stearyl acrylate, isobutene, Hexen-1, Diisobutene, Dodecen-1, Octadecen-1, Polyisobutenes with 15 up to 35 isobutene units, styrene, methyl vinyl ether, ethyl vinyl ether, octadecyl vinyl ether or mixtures thereof.

Crosslinking agents are also suitable as monomers (b) Monomers containing at least 2 ethylenically unsaturated, non-conjugated have double bonds in the molecule. Such connections are mostly in a relatively small amount together with water union monomers used to produce water-swellable polymers to deliver. Such copolymers are important, for example as water-absorbing polymers. The problem here is that you usually had to use water-soluble crosslinking agents to to produce uniform polymers. After the invention According to the method, it is also very difficult to dissolve in water or water-insoluble crosslinker homogeneously into the resulting ver wetted copolymer with a predominant proportion of water-soluble polymerize monomers. Suitable crosslinkers Component (b) are, for example, divinylbenzene, diallyl phthalate, allyl vinyl ether and / or diallyl fumarate. The water Soluble crosslinkers can be used alone or as homopolymers  together with water-soluble monomers to form copolymers be polymerized. If crosslinkers in the copolymerization of water-soluble monomers are used, the amount is of crosslinkers, based on those used in the polymerization Amounts of monomers, 0.05 to 10, preferably 0.1 to 2 wt .-%.

According to the Me. Known from the above prior art complexes are prepared from (a) and (b). So you can for example a cyclodextrin and / or a cyclodextrin structure ture containing compound and at least one monomer (b) ge dissolve together in a solvent and the solution if necessary heat. After removing the solvent, a kri remains stalliner complex. One molecule of compounds (a) can be up to contain two molecules of the monomers (b) bound in complex form. These complexes are referred to in the literature as host / guest complexes draws. The cyclodextrins or cyclodextrin structures ent holding compounds contain this in their cavities water-insoluble monomer of group (b).

The complexes from the compounds of groups (a) and (b) can can also be produced, for example, by one individual components (a) and (b) in a solvent that for example only the cyclodextrins and / or cyclodextrin structure Compounds containing compounds dissolves, but not the water soluble monomers. By heating, stirring, ultrasound treatment tion or other mechanical or thermal measures who accelerates the process of formation of the host / guest complexes the. Formation of Complexes from Compounds (a) and (b) is also possible in such a solvent that only the monomers ren (b) dissolves, but not the cyclodextrins. The complexes can even in the absence of solvents and thinners when the cyclodextrins and / or cyclodextrin structures ent holding compounds in a sufficiently fine distribution and brought into contact with the monomers (b). Furthermore it is possible to evaporate the monomers (b) and through the gas phase to act on the cyclodextrins. Such an ar example is in the production of complexes from cyclodextrins and low-boiling monomers (b) in particular prefers. So you can for example ethylene, propylene or iso Pass the butene over finely divided cyclodextrins. The formation of the Complexes can be at normal pressure, under reduced pressure or else be done under increased pressure. The molar ratio of Component (a): (b) is 1: 2 to 10: 1 and is preferably in the range of 1: 1 to 5: 1.  

The hydrophobic monomers (b) can be used alone or in a mixture are radically polymerized with one another. Besides, it is possible, at least one class of monomers (b) with water Lichen monomers to subject to copolymerization. Suitable water-soluble monomers, hereinafter referred to as group monomers (c) are, for example, monoethyleneic saturated C₃ to C₅ carboxylic acids, their amides and esters with amino alcohols of the formula

in which R = C₂ to C₅ alkylene, R¹, R², R³ = H, CH₃, C₂H₅, C₃H₇ and
X⊖ means an anion. Amides derived from amines of the formula are also suitable

deduce. The substituents in formula II and X⊖ have the same Meaning as in Formula I.

These compounds are, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, Fumaric acid, acrylamide, methacrylamide, crotonic acid amide, dimethyl aminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoneopen tylacrylate and dimethylaminoethyl methacrylate, dimethylamino propyl acrylate, dimethylaminoneopentyl acrylate and dimethylamino neopentyl methacrylate. The basic acrylates and methacrylates or basic amides, which differ from the compounds of formula II derived in the form of salts with strong mineral acids, Sulfonic acids or carboxylic acids or in quaternized form set. The anion X⊖ for the compounds of formula I is the Acid residue of the mineral acids or carboxylic acids or metho sulfate, ethosulfate or halide from a quaternizing agent.

Other water-soluble monomers of group (c) are N-vinyl pyrro lidon, N-vinylformamide, acrylamidopropanesulfonic acid, vinyl phosphonic acid and / or alkali or ammonium salts of vinyl sulfonic acid. The other acids can also either in not neutralized or in partial or up to 100% neutralized form can be used in the polymerization. Dial are also suitable as water-soluble monomers of group (c)  lylammonium compounds, such as dimethyldiallylammonium chloride, Diethyldiallylammonium chloride or diallylpiperidinium bromide, N-vinylimidazolium compounds, such as salts or quaternization products of N-vinylimidazole and 1-vinyl-2-methylimidazole, and N- Vinylimidazolines such as N-vinylimidazoline, 1-vinyl-2-methylimida zoline, 1-vinyl-2-ethylimidazoline or 1-vinyl-2-n-propylimidazo lin, also in quaternized form or as salt in the Polymerization can be used.

Preferred monomers of group (c) are monoethylenic saturated C₃ to C₅ carboxylic acids, vinyl sulfonic acid, acrylamido methylpropanesulfonic acid, vinylphosphonic acid, N-vinylformamide, Dimethylaminoethyl (meth) acrylates, alkali or ammonium salts mentioned monomers containing acid groups or mixtures of Monomers with each other. Of particular economic importance tion is the use of acrylic acid or mixtures of acrylic acid and maleic acid or their alkali salts in the manufacture of hydrophobically modified water-soluble copolymers.

To produce crosslinked polymers, for example as Superabsorbent or thickener for aqueous systems are used, at least one monomer is polymerized Group (c), for example acrylic acid, with at least one com plex ent from cyclodextrins and / or cyclodextrin structures holding connections and at least one class of ver wetting monomers having at least two ethylenic unsaturated, non-conjugated double bonds in the molecule point and are insoluble in water. The production of the network ten polymers can optionally additionally in the presence of Crosslinkers are made that are soluble in water and also via at least two ethylenically unsaturated, non-conjugated Double bonds in the molecule. Such monomers are for example N, N'-methylene-bisacrylamide, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate, each of polyethylene glycols with a molecular weight of 126 to 8500 deduce trimethylolpropane triacrylate, trimethylolpropane trimeth acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butane diol diacrylate, hexanediol diacrylate, hexanediol dimethacrylate, Diacrylates and dimethacrylates from block copolymers Ethylene oxide and propylene oxide, two or three times with acrylic acid or methacrylic acid esterified polyhydric alcohols such as Glycerin or pentaerythritol, triallylamine, tetraallylethylene diamine, trimethylol propane diallyl ether, pentaerythritol triallyl ether and / or N, N'-divinylethylene urea. The water soluble Crosslinkers are preferably used in amounts of 0.01 to 2.0% by weight,  based on the total used in the copolymerization Monomers.

The polymerization of water-insoluble monomers and given if the water-soluble monomers take place in the manner of a Solution or precipitation polymerization in an aqueous medium, preferably in water. Under an aqueous medium in the Mixtures of water and thus miscible organic liquids can be understood. Miscible with water organic liquids are, for example, glycols such as ethylene glycol, propylene glycol, block copolymers of ethylene oxide and Propylene oxide, alkoxylated C₁ to C₂₀ alcohols, acetic acid esters of glycols and polyglycols, alcohols such as methanol, ethanol, Isopropanol and butanol, acetone, tetrahydrofuran, dimethyl form amide, N-methylpyrrolidone or mixtures of the solvents mentioned medium. If the polymerization in mixtures of water and with Water-miscible solvents, the proportion is water-miscible solvents in the mixture up to 45% by weight. However, the polymerization is preferably carried out in water carried out.

The solution or precipitation polymerization of the monomers takes place usually in the absence of oxygen at temperatures of for example 20 to 200, preferably 35 to 140 ° C. The Polymerization can be carried out batchwise or continuously be performed. Preferably, at least a portion of the Monomers, initiators and optionally regulators during the Polymerization evenly into the reaction vessel. The monomes Ren and the polymerization initiator can, however, with smaller Batches are also placed in the reactor and polymerized, where if necessary, by cooling for a sufficiently rapid drove the heat of polymerization must worry.

The polymerization initiators used for radical poly connections usually used, which give radicals under the polymerization conditions, e.g. B. Peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxies ster, hydrogen peroxide and azo compounds. Examples of In itiators are hydrogen peroxide, dibenzoyl peroxide and dicyclohe xylperoxide dicarbonate, dilauryl peroxide, methyl ethyl ketone peroxide, Acetylacetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl per pivalate, tert-butyl perneohexanoate, tert-butylper-2-ethyl hexanoate, tert-butyl perbenzoate, lithium, sodium, potassium and Arnmonium peroxydisulfate, azoisobutyronitrile, 2,2'-azo bis (2-amidinopropane) dihydrochloride, 2- (carbamoylazo) isobutyro nitrile and 4,4′-azobis (4-cyanovaleric acid). The initiators  are usually in amounts up to 15, preferably 0.02 to 10 wt .-%, based on the monomers to be polymerized puts.

The initiators can be used alone or as a mixture with one another be used. Also the use of the well-known redox catalysts in which the reducing component in the molar Undershot is used. Known redox Catalysts are, for example, salts of transition metals such as Iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, copper (I) chloride, manganese-II-acetate, vanadium-III-acetate. As a redox Catalysts continue to have a reducing sulfur effect bonds such as sulfites, bisulfites, thiosulfates, dithionites and Tetrathionates of alkali metals and ammonium compounds or reducing phosphorus compounds in which phosphorus Has an oxidation number from 1 to 4, such as sodium hypo phosphite, phosphorous acid and phosphites.

In order to control the molecular weight of the polymers, the Polymerization if necessary in the presence of regulators to lead. Aldehydes such as form are suitable as regulators, for example aldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and iso butyraldehyde, formic acid, ammonium formate, hydroxylammonium sulfate and hydroxylammonium phosphate. Furthermore controllers can which contain sulfur in an organically bound form such as SH compounds containing organic compounds such as Thioglycol acetic acid, mercaptopropionic acid, mercaptoethanol, mercaptopropanol, mercaptobutanols, mercaptohexanol, dodecyl mercaptan and tert-dodecyl mercaptan. As a controller you can continue Salts of hydrazine such as hydrazine sulfate can be used. The Amounts of regulator, based on the monomers to be polymerized, are 0 to 20, preferably 0.5 to 15 wt .-%.

According to the invention, the polymerization can also be carried out in bulk leads. This is possible because the complexes from (a) and (b) are compatible with the water-soluble monomers, so that no phase separation occurs during the copolymerization.

Provided the water-insoluble monomers are used in the polymerization not in the form of complexes of cyclodextrins and water introduces soluble monomers of group (b) into the reactor the water-insoluble monomers (b) in an aqueous solution of cyclodextrins and / or cyclodextrin structures containing Add compounds and in the presence of polymerizationini tiators and optionally regulators of the polymerization fen. The water-insoluble Mo forms in the reaction medium nomeren (b) and the cyclodextrins and / or Cy present therein  Compounds containing host / guest complexes containing clodextrin structures from the manufacture of uniform homopolymers and copolymers allow. The cyclodextrins can also be mixed with water-soluble Mo Form nomeren host / guest complexes.

The polymers are optionally in the form of inclusion compounds ties before or can be obtained from them. The formation of Inclusion compounds from the polymers and the compounds of Component (a) is reversible. After the polymerization, the Polymers usually separate from the compounds (a). For example, copolymers of acrylic acid with contents on water-insoluble monoethylenically unsaturated compounds such as stearyl acrylate or polyisobutene of more than 20% by weight the aqueous reaction solution. If the polymers after the preparation in the form of inclusion compounds can NEN for example, by adding z. B. wetting agents such as ethoxylated long-chain alcohols to the reaction mixture the inclusion compounds are released and isolated. The Po modified hydrophobically by the process according to the invention Lymerisate can be used, for example, as a thickener, e.g. B. in cosmetic creams or lotions, as a component in lacquer form lulations, as sizing agents for papermaking, as loading Layering compound, as an adhesive raw material, as a detergent additive or can be used as dispersants for pigments. Farther can such polymers as tanning, retanning, fatliquoring or Water repellents can be used for leather production. Hy Drophobically modified polymers also serve as polymers Emulsifiers, which have a fine distribution of a non-polar substance in stabilize a polar phase. Cross-linked polyacrylic acids, the for example by copolymerizing acrylic acid in the presence at least one complex of cyclodextrin and a water soluble crosslinkers such as divinylbenzene are available as Superabsorbent or thickener for aqueous systems used.

Examples Production of complex I. Preparation of a complex of 2,6-dimethyl-β-cyclodextrin (DMCD) and N-hexyl methacrylamide in a molar ratio of 1: 1

6.4 g of N-hexyl methacrylamide were mixed with 50.0 g of 2,6-dimethyl-β-cyclo dextrin (DMCD) dissolved in 100 g chloroform and at room temperature stirred for 48 h. The solvent was distilled off and that  resulting product dried. It became a white solid product obtained in a yield of 96%.

Complexes II-IX

Analogously to the preparation of complex I, complexes of in Monomers indicated in the table with DMCD in a molar ratio of 1: 1 posed.

example 1 Homopolymerization of complex I

60.0 g of complex I of N-hexyl methacrylamide / DMCD are in 200.0 g of water dissolved. 0.25 g of potassium per sulfate and 0.10 g of potassium pyrosulfite (K₂S₂O₅) added. Under acid Exclusion of substance, the mixture was polymerized at 50 ° C. After The polymer formed was separated off and dried for 24 h. The polymer was obtained in 94% yield.

Examples 2 to 6

Homopolymers of complexes II to VI were prepared in analogy to Example 1 prepared. The yields are in the following Ta belle specified.

Example 7 Copolymerization of complex I with acrylic acid (1: 1 molar)

60.0 g of complex I of N-hexyl methacrylamide / DMCD and 2.8 g Acrylic acid is dissolved in 200.0 g of water. Become the solution 0.25 g of potassium persulfate and 0.10 g of potassium pyrosulfite (K₂S₂O₅) against ben. In the absence of oxygen, the mixture was at 50 ° C. polymerized. After 24 hours, the polymer formed was separated and dried it. The polymer was obtained in a yield of 91% receive.

Examples 8-12

The complexes II, V, VII, VIII and IX were analogous to Bei game 7 with the monomers given in the following table polymerized.

Claims (8)

1. A process for the preparation of polymers from water-insoluble monomers and optionally water-soluble monomers by radical polymerization of the monomers in a diluent, characterized in that the polymerization is carried out in water as a diluent and the water-insoluble monomers in the form of complexes

• (a) Cyclodextrins and / or cyclodextrin structures containing compounds and
• (b) water-insoluble or at most up to 20 g / l at 20 ° C water-soluble ethylenically unsaturated monomers

in the molar ratio (a): (b) from 1: 2 to 10: 1 or the monomers in the presence of up to 5 mol, based on 1 Mol of the monomers (b), of cyclodextrins and / or cyclodex Compounds containing trin structures polymerized. 2. The method according to claim 1, characterized in that one as monomers (b) C₂ to C₃₀ alkyl esters of acrylic acid, C₁- to C₃₀-alkyl esters of methacrylic acid, C₂- to C₃₀-α-olefins, C₁ to C₂₀ alkyl vinyl ether, styrene, butadiene, isoprene or uses their mixtures. 3. The method according to claim 1 or 2, characterized in that crosslinking monomers are used as monomers (b), the at least two ethylenically unsaturated, not konju have double bonds in the molecule. 4. The method according to claim 1 or 2, characterized in that as monomers (b) butyl acrylate, lauryl acrylate, methyl meth acrylate, stearyl acrylate, isobutene, hexene-1, diisobutene, Dodecen-1, Octadecen-1, polyisobutene with 15 to 35 isobutene Units, styrene, methyl vinyl ether, ethyl vinyl ether, octa decyl vinyl ether or mixtures thereof. 5. The method according to claim 3, characterized in that one as crosslinking monomers divinylbenzene, diallyl phthalate, allyl vinyl ether and / or diallyl fumarate.   6. The method according to claims 1 to 5, characterized in net that monoethylene as water-soluble monomers unsaturated C₃ to C₅ carboxylic acids, vinyl sulfonic acid, acrylic amidomethylpropanesulfonic acid, vinylphosphonic acid, N-vinylfor mamide, dialkylaminoethyl (meth) acrylates, alkali or Ammonium salts of the monomers mentioned acid groups ren or mixtures of the monomers used with each other. 7. The method according to claim 1, characterized in that one as water-soluble monomers acrylic acid, mixtures of acrylic acid and maleic acid or the alkali salts of the mo nomeren uses.