DE10027745A1 - Production of fluorinated polymers in aqueous solution comprises complexing at least one polymerizable fluorinated olefinic monomer, an initiator and/or non-fluorinated comonomers in the presence of cyclodextrin. - Google Patents

Abstract

A process for the production of fluorinated polymers in aqueous solution comprises complexing at least one polymerizable fluorinated olefinic monomer, an initiator and/or non-fluorinated comonomers in the presence of cyclodextrin. A process for the production of fluorinated polymers in aqueous solution comprises complexing at least one of the components (A)-(C) in the presence of cyclodextrin. (A) at least one polymerizable fluorinated monomer of formula (1)-(3); (B) an initiator; and (C) non-fluorinated comonomers. R<1> = H, F, 1-4C alkyl or trifluoromethyl; R<2> = H, F, 1-4C alkyl, COOM, SO3M or 1-4C fluorinated alkoxy; M = H or alkali metal; R<3> = H, F, Cl or 1-4C alkyl, trifluoromethyl or hydroxymethyl; R<4> = 1-4C alkyl or 2-18C monocarboxylic acid group; X1, X2 = F, Cl or H; X3 = F, Cl, H, CN, COOR<5>, CONR<6>R<7> or COR<8>; R<5> = H, 1-18C fluorinated alkyl, 1-18C alkyl optionally substituted by OH, OR<5> or NR<6>R<7>; R<6>, R<7> = H, 1-18C alkyl or together form a 5-12C cycloalkyl; R<8> = 1-18C alkyl, phenyl, fluorophenyl or 5-12C cycloalkyl, optionally at least partially fluorinated in the alkyl groups;

Description

The invention relates to a process for the preparation of fluorinated polymers Polymerization of olefinically unsaturated fluorinated monomers in the presence of cyclodextrins in aqueous solution, in particular of cyclodextrin complexed olefinically unsaturated fluorinated monomers in aqueous solution without the addition of emulsifiers or "surfactants".

The class of compounds of fluorinated polymers includes those by polymerization of Polymers that can be produced by olefinically unsaturated fluorinated monomers Homopolymerization or copolymerization of olefinically unsaturated fluorinated Monomers with possibly other, non-fluorinated monomers are obtained.

The fluorinated polymers are used for non-stick coatings, textiles, Cement, concrete etc. and as an additive to silicones to make the water-repellent and oil-repellent increase impact. The fluorinated polymers also adhere to hydro phobic surfaces (e.g. on polytetrafluoroethylene).

The fluorinated polymers are usually produced industrially by radical polymerization in bulk, in an organic solvent or in Emulsion.

Due to the insolubility of the monomeric compounds in water, the Process an emulsifier and / or an organic cosolvent are added. The Polymerization takes place under the conditions of the emulsion polymerization or in organic solvents or solvent mixtures in the presence of a fluorinated "surfactant".

Another disadvantage that exists in the manufacture of fluorinated polymers is that due to the insolubility of the olefinically unsaturated fluorinated monomers  in water, often when using water-soluble monomers in solution medium mixtures must be worked, mostly from organic and often fluorinated solvents exist.

Solid monomers usually cannot emulsions at all in aqueous medium be polymerized.

The radical polymerization of acrylates, methacrylates and vinyl compounds solutions in aqueous solutions in the presence of cyclodextrins is known. In the DE-A 195 33 269 (Macromolecules 32 (1999) 5236-5239) is the free radical Polymerization of (meth) acrylates complexed with cyclodextrin in aqueous Solution examined. In documents EP-A 0 896 027, EP-A 0 780 401, DE-A 195 48 038 and EP-A 0 853 092 describe emulsion polymerization or Suspension polymerization of vinyl compounds and / or (meth) acrylates in aqueous solution described in the presence of cyclodextrins.

The emulsion polymerization of fluorinated monomers with at least one non-fluorinated water-soluble or water-insoluble monomer in the presence of cyclodextrins and a "surfactant" is disclosed in EP-A 0 890 592. Leibler et al. (Science 285 (1999) 1246) describe the copolymerization of Perfluorooctyl acrylate with a methacrylate in butyl acetate.

However, none of the publications mentioned reports on the possibility of emulsifier-free or "surfactant" -free polymerization and / or copolymerization of olefinically unsaturated fluorinated monomers in the presence of cyclo dextrins in aqueous solution.

The object of the present invention was therefore to provide a method for emulsifier-free or "surfactant" -free polymerization in aqueous solution, without to provide the disadvantages described.  

Furthermore, there are technically advantageous polymerization processes that are in water to be carried out, for environmental protection reasons and workplace hygiene aspects ten and desirable for reasons of resource conservation.

It has now been found that by complexing the olefinically unsaturated fluorinated monomeric compounds with cyclodextrins (CD) and / or com plexing the initiator system and / or complexing the non-fluorinated Co monomeric the disadvantages mentioned above in the polymerization in water can be avoided and products with improved quality result.

It is thus possible to use the method according to the invention to emulsifier-free or solvent free polymers by polymerizing fluorinated monomers in to produce aqueous solution. Water-insoluble initiators and initiator systems can be converted into water-soluble forms with cyclodextrins.

The invention thus relates to a process for the preparation of fluorinated polymers in aqueous solution, characterized in that at least one component is selected from

• A) one or more polymerizable fluorinated monomers of the formulas (I), (II) and / or (III),
  in which
  R ^{1 is} hydrogen, fluorine, C ₁ -C ₄ alkyl or trifluoromethyl,
  R ^{2 is} hydrogen, fluorine or (fluoro) alkyl with 1 to 4 carbon atoms in the ortho, meta or para position, COOM or SO ₃ M (M = H, alkali metal), or (fluoro) alkoxy with 1 to 4 C- Atoms,
  R ^{3 is} hydrogen, fluorine or chlorine, C ₁ -C ₄ alkyl, trifluoromethyl, hydroxymethyl,
  R ^{4 is} C ₁ -C ₄ alkyl or the residue of a C ₂ -C ₁₈ monocarboxylic acid, and
  X ₁ fluorine, chlorine or hydrogen,
  X ₂ fluorine, chlorine or hydrogen,
  X _{3 represents} fluorine, chlorine, hydrogen, CN- (cyano), COOR ⁵ - (ester), CONR ⁶ R ⁷ - (amide) or COR ⁸ - (keto) group, where
  R ^{5 is} hydrogen, (fluoro) alkyl with C ₁ -C ₁₈ alkyl, a C ₁ -C ₁₈ alkyl group which can be substituted with OH or OR ⁵ or NR ⁶ R ⁷ ,
  R ⁶ and R ^{7 are} independently hydrogen or C ₁ -C ₁₈ alkyl or together C ₅ - C ₁₂ cycloalkyl, and
  R ^{8 represents} a C ₁ -C ₁₈ alkyl, phenyl, fluorophenyl or C ₅ -C ₁₂ cycloalkyl,
  where hydrogen in the alkyl radicals is partially or completely replaced by fluorine or chlorine,
• B) initiator and
• C) non-fluorinated comonomer or mixture of non-fluorinated Co monomeric

Cyclodextrin are complexed.

Examples of polymerizable, monounsaturated fluorinated vinyl compounds are 2,3,4,5,6-pentafluorostyrene, α-trifluoromethyl vinyl acetate, 1H, 1H-pentafluoro propyl acrylate, 1H, 1H-pentafluoropropyl methacrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl methacrylate, perfluorooctyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, Chlorotrifluoroethylene, 1,1-dichloro-2,2-difluoroethylene, 1,2-dichloro-1,2-difluoroethylene, Fluorotrichlorethylene, 2-chloro-1,1-difluoroethylene, 1,2-dichloro-1-fluoroethylene, 1,1- Difluoroethylene, trifluoroethylene, tetrafluoroethylene, vinyl fluoride, hexafluoropropene, 3- Fluoropropene, 1,1,3,3,3-pentafluoropropene-1.

Preferred fluorinated monomers are 1H, 1H-pentafluoropropyl acrylate, 1H, 1H- Pentafluoropropyl methacrylate, 1H, 1H, 2H, 2H-perfluorooctyl methacrylate, 1H, 1H, 2H, 2H perfluorodecyl methacrylate.

Several monomers can be copolymerized in the process according to the invention be, wherein at least one of the monomers (at least 1 wt .-% of all set monomers) from the group of fluorinated monomers, at least one of the monomers is complexed and the other comonomers depending on Intended use of the product Cyclodextrin-complexed or uncomplexed can be used.

Examples of F-free comonomers are vinyltoluene, α-methylstyrene, styrene, acrylic nitrile, (meth) acrylic acid methyl ester and higher (meth) acrylic acid alkyl ester with 2 to 18 carbon atoms in the alkyl radical, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, styrene sulfonic acid and its sodium salt, 4-styrene carboxylic acid, methacrylic acid,  2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, vinyl acetate, vinyl ester of Versatic acid, vinyl ether, butadiene, isoprene, chloroprene, Vinyl pyridine.

Preferred non-fluorinated monomers are styrene, acrylonitrile, stearyl methacrylate, Stearyl acrylate, butadiene, isoprene, chloroprene, methyl methacrylate, hydroxy ethyl methacrylate, sodium styrene sulfonate, vinyl pyridine.

Another object of the invention is the use of cyclodextrin com plexed olefinically unsaturated fluorinated monomers for copolymerization with other water-soluble or water-insoluble monomers, which if necessary can be complexed with cyclodextrins.

Cyclodextrins are cycloamyloses with 1,4-linked glucose units as they are when starch is broken down by Bacillus macerans or Bacillus circulans under Ein Effect of cyclodextrin glycosyltransferase arise, for. B. Cyclohexa-, Cyclo hepta- or cyclooctaamyloses with 6, 7 or 8 cyclically linked glucose units (α-, β-, γ-cyclodextrin).

Methods for producing cyclodextrins are known and, for example, be wrote in "Römpp's Lexikon Chemie", 10th edition, Stuttgart / New York 1997, Pp. 845 ff and Chemical Reviews 98 (1998), pp. 1743 ff.

Cyclodextrins used in the manufacture of monomer / cyclodextrin complexes and / or complexation of the metal / ligand catalysts and / or complexation the initiators come into question are e.g. B. substituted or unsubstituted Cyclodextrins and their esters, alkyl ethers, hydroxyalkyl ethers, alkoxycarbonyl alkyl ethers and carboxyalkyl ethers or their salts.

Suitable carboxylic acid components for the cyclodextrin esters are aryl, aralkyl and alkyl carboxylic acids, particularly preferred are aralkyl and alkyl carboxylic acids  preferably alkyl carboxylic acids. Suitable alkyl carboxylic acids are those with 2 to 30 Carbon atoms, preferably with 2 to 24 carbon atoms, particularly preferably with 2 to 18 carbon atoms Atoms.

The mono-, di- or triether or mono-, di- or triester or monoester diether are generally by etherification of α-, β- and γ-cyclodextrins with alkylly agents such as dimethyl sulfate or alkyl halides with 1 to 30 C atoms and / or esterification with z. B. acetic acid, higher monocarboxylic acids (Fatty acids) or succinic acid.

As an alkyl component for the cyclodextrin alkyl ether, hydroxyalkyl ether, alkoxy carbonyl alkyl ethers and carboxyalkyl ethers come in linear or branched form optionally substituted alkyl groups with 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms Atoms, particularly preferably 1 to 18 carbon atoms in question.

Preferred cyclodextrins are α-, β- and γ-cyclodextrin, partially or completely acetylated, methylated, hydroxylated and succinylated α-, β- and γ-cyclo dextrin, as well as mixed methylated and acetylated β-cyclodextrins. Especially β-cyclodextrin, 2,6-dimethyl-β-cyclodextrin and (2-hydroxy) are preferred propyl-β-cyclodextrin.

All radicals described in the prior art are suitable as initiators initiators, such as B. radical or radical-forming compounds or substance mixtures, such as hydroperoxides, organic peroxides or inorganic peroxides. Ammonium, sodium and potassium persulfate, potassium peroxodisulfate, and azo compounds such as 2,2'-azobis (2- (2-imidazolin-2-yl) propane) dihydro chloride, 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide), dimethyl-2,2'- azobis isobutyrate, 4,4'-azo-bis-4-cyanopentanoic acid. Are particularly preferred Redox systems such as potassium peroxodisulfate / sodium bisulfite or dibenzoyl peroxide / N, N-dialkylaniline.  

Water-insoluble or poorly water-soluble radical initiators, such as Azobis (isobutyronitrile) (AIBN), tertiary butyl perbenzoate or dibenzoyl peroxide can be converted into a water-soluble form with cyclodextrins. Water Insoluble or sparingly water-soluble initiators are preferably used in com plexed form used.

Examples of water-soluble initiators are 2,2'-azobis (N, N'-di-methylene-iso butyramidine) dihydrochloride or 2,2'-azobis (2-amidinopropane) dihydrochloride.

The aqueous phase of the process according to the invention may be minor Proportions (0 to 10%) of soluble organic substances such as short-chain alcohols, Contain acetone or urea. Finally, the method according to the invention also suitable for polymerization in the presence of insoluble components such as Pigments, fillers or fibers (glass fibers, C fibers).

Any water-soluble salts such as NaCl, Na ₂ SO ₄ , CaCl ₂ , NaF, NaNO ₃ or various additives based on water-soluble polymers, such as cellulose derivatives such as methyl cellulose, carboxy methyl cellulose, polyvinyl alcohol, polyvinylamine or polyhydroxyethyl methacrylate, can be present in the aqueous phase .

The monomer or monomers are in an equimolar ratio of Complexed monomer / cyclodextrin.

The copolymerization of the complexed monomer with one or more Complexed or uncomplexed comonomers can be used in variable molar ver Ratios between the different monomers are carried out.

The reaction conditions of radical polymerization are generally known (cf. prior art mentioned above).

example 1 Preparation of a 1H, 1H pentafluoropropyl methacrylate / cyclodextrin com plexes

1.0 g (4.58 mmol) of 1H, 1H-pentafluoropropyl methacrylate were dissolved in 12.7 g of an aqueous solution consisting of 6.1 g (4.58 mmol) of methylated β-cyclodextrin (m-β-CD, Cavasol® W7 M, Wacker Chemie GmbH, Munich, Germany) and 6.6 g of nitrogen-inert water in a N ₂ atmosphere with vigorous stirring or ultrasound at room temperature within 15 minutes in a clear and homogeneous solution.

Example 2 Preparation of a 1H, 1H, 2H, 2H perfluorooctyl methacrylate / cyclodextrin com plexes

1.0 g (2.3 mmol) of 1H, 1H, 2H, 2H-perfluorooctyl methacrylate were dissolved in 6.4 g of an aqueous solution consisting of 3.08 g (2.3 mmol) of methylated β-cyclodextrin (m-β- CD, Cavasol® W7 M, Wacker Chemie GmbH) and 3.32 g of water inertized with nitrogen under N ₂ atmosphere with vigorous stirring or ultrasound at room temperature within 15 min and homogeneously dissolved.

Example 3 Preparation of a 1H, 1H, 2H, 2H perfluorodecyl methacrylate / cyclodextrin com plexes

2.0 g (3.76 mmol) of 1H, 1H, 2H, 2H-perfluorodecyl methacrylate were dissolved in 10.4 g of an aqueous solution consisting of 5.0 g (3.76 mmol) of methylated β-cyclodextrin (m-β-CD, Cavasol® W7 M, Wacker Chemie GmbH) and 5.4 g of water inertized with nitrogen under N ₂ atmosphere with vigorous stirring or ultrasound at room temperature within 15 min and homogeneously dissolved.

Example 4 Radical homopolymerization of a 1H, 1H pentafluoropropyl methacrylate / Cyclodextrin complex with a water-soluble redox initiator

0.062 g (0.229 mmol) of K ₂ S ₂ O ₈ and 0.024 g (0.229 mmol) of NaHSO _{3 were} added to the 1H, 1H pentafluoropropyl methacrylate / cyclodextrin complex solution prepared in Example 1 under an N ₂ atmosphere. This solution was polymerized with stirring at a temperature of 60 ° C for 95 min. The precipitated polymer was filtered off, washed with methanol and dried in vacuo.
Yield: 1 g (100% of theory)
Glass transition temperature: Tg = 69.5 ° C.

Example 5 Radical homopolymerization of a 1H, 1H pentafluoropropyl methacrylate / Cyclodextrin complex with a water-soluble azo initiator

To the 1H, 1H pentafluoropropyl methacrylate / cyclodextrin complex solution prepared in Example 1 was added 0.074 g (0.229 mmol) of 2,2'-azobis (N, N'-di-methylene-isobutyramidine) dihydrochloride under an N ₂ atmosphere. This solution was polymerized with stirring at a temperature of 60 ° C for 95 min. The precipitated polymer was filtered off, washed with methanol and dried in vacuo.
Yield: 0.944 g (94.4% of theory)
Glass transition temperature: Tg = 69.5 ° C.

Example 6 Radical homopolymerization of a 1H, 1H, 2H, 2H-tridecafluorooctyl meth acrylate / cyclodextrin complex with a water-soluble redox initiator

0.031 g (0.115 mmol) of K ₂ S ₂ O ₈ and 0.012 g (0.115 mmol) of NaHSO _{3 were} added to the 1H, 1H, 2H, 2H-tridecafluorooctyl methacrylate / cyclodextrin complex solution prepared in Example 2 under an N ₂ atmosphere. This solution was polymerized with stirring at a temperature of 60 ° C for 95 min. The precipitated polymer was filtered off, washed with methanol and dried in vacuo.
Yield: 0.966 g (96.6% of theory)
Glass transition temperature: Tg = 35 ° C.

Example 7 Radical homopolymerization of a 1H, 1H, 2H, 2H-tridecafluorooctyl meth acrylate / cyclodextrin complex with a water-soluble azo initiator

0.037 g (0.115 mmol) of 2,2'-azobis (N, N'-di-methylene-isobutyramidine) was added to the 1H, 1H, 2H, 2H-tridecafluorooctyl methacrylate / cyclodextrin complex solution prepared in Example 2 under an N ₂ atmosphere. given dihydrochloride. This solution was polymerized with stirring at T = 60 ° C for 95 min. The precipitated polymer was filtered off, washed with methanol and dried in vacuo.
Yield: 0.783 g (78.3% of theory)
Glass transition temperature: Tg = 35 ° C.

Example 8 Radical homopolymerization of a 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate / cyclodextrin complex with a water-soluble redox initiator

0.051 g (0.188 mmol) of K ₂ S ₂ O ₈ and 0.020 g (0.188 mmol) of NaHSO _{3 were} added to the 1H, 1H, 2H, 2H-perfluorodecyl methacrylate / cyclodextrin complex solution prepared in Example 3 under an N ₂ atmosphere. This solution was polymerized with stirring at T = 60 ° C for 95 min. The precipitated polymer was filtered off, washed with methanol and dried in vacuo.
Yield: 1.96 g (98% of theory)

Example 9 Radical homopolymerization of a 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate / cyclodextrin complex with a water-soluble azo initiator

0.061 g (0.188 mmol) of 2,2'-azobis (N, N'-di-methylene-isobutyramidine) was added to the 1H, 1H, 2H, 2H-perfluorodecyl methacrylate / cyclodextrin complex solution prepared in Example 3 under an N ₂ atmosphere. given dihydrochloride. This solution was polymerized with stirring at T = 60 ° C for 95 min. The precipitated polymer was filtered off, washed with methanol and dried in vacuo.
Yield: 1.5 g (75% of theory)

Example 10 (comparison) Radical homopolymerization of non-complexed 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate in water with a water soluble Redox initiator

2 g (3.76 mmol) of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate were added to 12 ml of degassed water and 0.02 g (0.188 mmol) of K ₂ S ₂ O ₈ and 0.020 g (0.188 mmol) under an N ₂ atmosphere. NaHSO ₃ added. This mixture was polymerized under the same conditions as in Example 9 (same stirring speed, T = 50 ° C., t = 95 min). The polymer formed in small amounts was filtered off, washed with methanol and dried in vacuo.
Yield: 0.018 g (0.9% of theory)

Example 11 Radical copolymerization of a 1H, 1H-pentafluoropropyl methacrylate / Cyclodextrin complex with a styrene / cyclodextrin complex using a water-soluble redox initiator

0.5 g (2.3 mmol) of 1H, 1H-pentafluoropropyl methacrylate and 0.562 g (5.4 mmol) of styrene were dissolved in 21.4 g of an aqueous solution consisting of 10.25 g (7.7 mmol) of methylated β- Cyclodextrin (m-β-CD, Cavasol® W7 M, Wacker Chemie GmbH) and 11.15 g of nitrogen-inert water in a N ₂ atmosphere with vigorous stirring or ultrasound at room temperature within 15 min in a clear and homogeneous solution. Then 0.104 g (0.385 mmol) of K ₂ S ₂ O ₈ and 0.04 g (0.385 mmol) of NaHSO _{3 were} added under an N ₂ atmosphere and the mixture was polymerized at T = 50 ° C. for 95 minutes with stirring. The precipitated copolymer was filtered off, washed with methanol and dried in vacuo.
Yield: 1.06 g (100% of theory)
Glass transition temperature: Tg = 80 ° C.

Example 12 Radical copolymerization of a 1H, 1H, 2H, 2H-tridecafluorooctyl meth acrylate / cyclodextrin complex with a styrene / cyclodextrin complex With the help of a water-soluble redox initiator

1 g (2.3 mmol) of 1H, 1H, 2H, 2H-perfluorodecyl methacrylate and 0.562 g (5.4 mmol) of styrene were methylated in 21.4 g of an aqueous solution consisting of 10.25 g (7.7 mmol) β-Cyclodextrin (m-β-CD, Cavasol® W7 M, Wacker Chemie GmbH) and 11.15 g of water inert with nitrogen under a N ₂ atmosphere with vigorous stirring or ultrasound at room temperature within 15 min. Then 0.0845 g (0.313 mmol) of K ₂ S ₂ O ₈ and 0.033 g (0.313 mmol) of NaHSO _{3 were} added under an N ₂ atmosphere and the mixture was polymerized at T = 50 ° C. for 95 minutes with stirring. The precipitated copolymer was filtered off, washed with methanol and dried in vacuo.
Yield: 1.55 g (99.2% of theory)
Glass transition temperatures: Tg1 = 55 ° C and Tg2 = 80 ° C.

Example 13 Radical copolymerization of a 1H, 1H, 2H, 2H-heptadecafluorodecylmeth acrylate / cyclodextrin complex with a styrene / cyclodextrin complex With the help of a water-soluble redox initiator

1 g (1.88 mmol) of 1H, 1H, 2H, 2H-perfluorodecyl methacrylate and 0.456 g (4.38 mmol) of styrene were methylated in 17.4 g of an aqueous solution consisting of 8.33 g (6.26 mmol) β-cyclodextrin (m-β-CD, Cavasol® W7 M, Wacker Chemie GmbH) and 9.07 g of water inert with nitrogen under an N ₂ atmosphere with vigorous stirring or ultrasound at room temperature within 15 min. Then 0.0845 g (0.313 mmol) of K ₂ S ₂ O ₈ and 0.033 g (0.313 mmol) of NaHSO _{3 were} added under an N ₂ atmosphere and the mixture was polymerized at T = 50 ° C. for 95 minutes with stirring. The precipitated copolymer was filtered off, washed with methanol and dried in vacuo.
Yield: 1.39 g (95.5% of theory)
Glass transition temperatures: Tg1 = 65 ° C and Tg2 = 91 ° C.

The glass transition temperature was determined by means of DSC (differential scanning Colorimetry) at a heating rate of 20 ° C / min under nitrogen.

Claims (10)

1. A process for the preparation of fluorinated polymers in aqueous solution, characterized in that at least one component is selected from

• A) one or more polymerizable fluorinated monomers of the formulas (I), (II) and / or (III),
  in which
  R ^{1 is} hydrogen, fluorine, C ₁ -C ₄ alkyl or trifluoromethyl,
  R ^{2 is} hydrogen, fluorine or (fluoro) alkyl with 1 to 4 carbon atoms in the ortho, meta or para position, COOM or SO ₃ M (M = H, alkali metal), or (fluoro) alkoxy with 1 to 4 C- Atoms,
  R ^{3 is} hydrogen, fluorine or chlorine, C ₁ -C ₄ alkyl, trifluoromethyl, hydroxy methyl,
  R ^{4 is} C ₁ -C ₄ alkyl or the residue of a C ₂ -C ₁₈ monocarboxylic acid, and
  X ₁ fluorine, chlorine or hydrogen,
  X ₂ fluorine, chlorine or hydrogen,
  X _{3 represents} fluorine, chlorine, hydrogen, CN- (cyano), COOR ⁵ - (ester), CONR ⁶ R ⁷ - (amide) or COR ⁸ - (keto) group, where
  R ^{5 is} hydrogen, (fluoro) alkyl with C ₁ -C ₁₈ alkyl, a C ₁ -C ₁₈ alkyl group which can be substituted with OH or OR ⁵ or NR ⁶ R ⁷ ,
  R ⁶ / R ^{7 are} independently hydrogen or C ₁ -C ₁₈ alkyl or together C ₅ -C ₁₂ cycloalkyl, and
  R ^{8 is} a C ₁ -C ₁₈ alkyl, phenyl, fluorophenyl or C ₅ -C ₁₂ cyclo alkyl,
  where hydrogen in the alkyl radicals is partially or completely replaced by fluorine or chlorine,
• B) initiator and
• C) non-fluorinated comonomer or mixtures of non-fluorinated co-monomers,

Cyclodextrin are complexed. 2. The method according to claim 1, characterized in that at least one fluorinated monomer selected from the group 1H, 1H-pentafluoropropyl acrylate, 1H, 1H-pentafluoropropyl methacrylate, 1H, 1H, 2H, 2H-perfluorooctyl methacrylate, 1H, 1H, 2H, 2H-perfluorodecyl methacrylate is polymerized.   3. The method according to claim 1, characterized in that cyclodextrin-kom plexed olefinically unsaturated fluorinated monomers and cyclodextrin complexed fluorine-free monomers can be used. 4. The method according to claim 1, characterized in that a non-fluorinated Comonomer selected from the group of compounds vinyltoluene, α- Methylstyrene, styrene, acrylonitrile, (meth) acrylic acid methyl ester and (meth) - Acrylic acid alkyl esters with 2 to 18 carbon atoms in the alkyl radical, hydroxy ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, styrene sulfonic acid and her Sodium salt, 4-styrene carboxylic acid, stearyl methacrylate, stearyl acrylate, meth acrylic acid, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, vinyl acetate, vinyl ester of Versatic acid, vinyl ether, butadiene, Isoprene, chloroprene or vinyl pyridine is polymerized. 5. The method according to claim 1, characterized in that the cyclodextrins be selected from at least one from the group of substituted or unsubstituted cyclodextrins and their esters, alkyl ethers, hydroxy alkyl ethers, alkoxycarbonylalkyl ethers and carboxyalkyl ethers or their Salts. 6. The method according to claim 5. characterized in that the cyclodextrins be selected from at least one from the group of α-, β- and γ- Cyclodextrins, partially or fully acetylated, methylated, hydroxy lated and succinylated α-, β- and γ-cyclodextrins, and mixed methy lated and acetylated β-cyclodextrins. 7. The method according to claim 6, characterized in that the cyclodextrins are selected from at least one from the group of β-cyclo dextrins such as 2,6-dimethyl-β-cyclodextrin or (2-hydroxy) propyl-β-cyclo dextrin.   8. The method according to claim 1, characterized in that the initiators be selected from at least one from the group of radicals or radical-forming compounds or mixtures of substances. 9. The method according to claim 8, characterized in that the initiators be selected from at least one from the group of compounds such as ammonium, sodium and potassium persulfate, potassium peroxodisulfate, as well as azo compounds such as 2,2'-azobis (2- (2-imidazolin-2-yl) propane) di hydrochloride, 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide), Di methyl 2,2'-azobis isobutyrate, 4,4'-azo-bis-4-cyanopentanoic acid. 10. The method according to claim 9, characterized in that the initiators selected from at least one from the group of redox systems such as potassium peroxodisulfate / sodium bisulfite or dibenzoyl peroxide / N, N-dialkylaniline.