DE2429399A1 - FLUORINATED ACRYLIC ACID ESTERS AND THEIR POLYMERIZATION PRODUCTS - Google Patents

Description

CI3A-GE1QY AG, CH-4002 3ase!

Case 1-8854 / +

Germany

Fluorinated acrylic acid esters and their polymerization products

From the French patent 1 535 fluorinated acrylic esters are known, for example the formulas

, -RXH ₀ CHCh ₀ OOCCH = CH ₉ ·

. and

RXH ₀ CH-OOCC-CH ₀ . ^{f 2} II CH ₀ OH R

correspond. R ^ is a perfluoroalkyl radical with 3 to Carbon atoms, while R is hydrogen or methyl,

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The polymers of these acrylic acid derivatives are used to treat a wide variety of materials.

U.S. Patent 3,455,996 describes a process for the preparation of acrylic acid esters !!, which are obtained are by reaction of vicinal alkylene oxides with 3 to 4 carbon atoms, the alkyl substituents with up to 'two Contain carbon atoms and at least two halogen atoms, with acrylic or methacrylic acid. Aluminum isopropoxide is used as the catalyst for the reaction.

The present invention now relates to polymerization products of at least one fluorinated one Acrylic acid esters of the formula

R - CH - CH - OC - C = CH ₀ Ii B ■ ^L OH R ₂ 0

where R is a perfluorinated aliphatic hydrocarbon radical having 3 to 22 carbon atoms and R 1 and R «are hydrogen or methyl and optionally other copolymerizable, ethylenically unsaturated, monomeric compounds.

The perfluorinated hydrocarbon radical in formula (1) "can be, for example, a straight-chain or branched perfluoroalkyl radical with 4 to 17 carbon atoms and roughly correspond to the following formulas:

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) - P = 4-17

(CF ₃ ) 2 ^CF. < ^CF ₂ V ^{q = Χ} " ¹⁴

CF ₃ [CF ₂ CF (CF ₃ )] _r - r = 1-4

(CF ₃ ) ₂ CF [CF ₂ CF (CF ₃ )] _s -S = 1-4

There are also o-H-perfluoroalkyl radicals in Be costume.

Preferably, the fluorinated acrylic acid esters of the formula

^<2> "V ₂ IH-I ¹¹ - CH - OC - C = CH ₂ OH R ₂ 0

where R ₁ and R _{0 are} hydrogen or methyl and η is an integer from 4 to 14.

The compounds of the formulas are also of particular interest

(3) CH _o ",, CH - CH - OC - C = CH ₉ ^v - 'η, 2η _Ί +1 | ι κ 2

^xx OH R ₂ 0

(4) CH ₀ , -GH - CH ₀ - 0 r C - CH = CH ₀ ^x 'n _T ^ n ₁ +! j 2 \\ L

^L - OH 0

(5) CH ₀ ■ _n CH - CH ₀ - 0 - C - C = CH ₀ , η-, 2η _Ί +1 | 2 μ,

^x - - ■ OH ■ 0 CH ₃ ·

■ 40 9 8 8-4 / 1 298

(6) CH ₀ ,, CH - CH - O - C - CH - CH ₀ ^v nj zn, + 1 | ι ο 2

OH CHo 0

and

(7) CH ₀ ,, CH - CH - 0 - C - C = CH ₀ ,

η, 2η, + 11 ι Ii ι 2

^{1 L} OH CH ₃ O CH ₃

where R, and R "are hydrogen or methyl and n, is an integer from 6 to 12.

The fluorinated ones according to the invention are produced Acrylic acid esters by adding perfluoroalkyl epoxides or -Glycols of the formulas

(8) R-CH-CH-R ₂ and (9) R-CH-CH-R ₂

0 OH OH

with acrylic acid, methacrylic acid or their anhydrides.

For the esterification one uses e.g. the glycol. of the formula (9) with an anhydride of the acids mentioned, preferably however, epoxides of the formula (8) with the acids mentioned or their salts.

The perfluoroalkyl epoxies or glycols used preferably contain straight-chain or branched perfluoroalkyl radicals with 4 to 17 carbon atoms. If necessary, mixtures, i.e. epoxies or glycols with different Chain length are used in the perfluoroalkyl radicals. These mixtures exist when the starting materials

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for the epoxies or glycols by telomerization processes getting produced.

Particularly suitable epoxides now correspond to the formulas

/ - ^R 2>

where R «is hydrogen or methyl and η is an integer of 4 to 14, and

v - ^R

where R ^ has the meaning given and n is an integer is from 6 to 12.

The reaction of the epoxies with the unsaturated acids can, for example, in the presence of 0.01 to 2.0 moles of one Amine, based on the molar amount of the epoxide, take place as a catalyst.

The ammonium, amine or alkali salts can also be used the acrylic or methacrylic acid can be used.

For example, the following amines are included in the. Reaction can be used: lower alkyl amines with 1 to 4 carbon atoms in the alkyl radical, such as triethylamine, triethylamine, Tributylamine; also N-methylpiperidine, N-methylmorpholine,

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N.N-dimethylcyclohexylamine, Ν, Ν-dimethyl-benzylamine, pyridine, Quinoline, N.N-dimethylaniline, diazabicyclooctane, etc.

The reaction can be carried out in solvents or else without a solvent. Solvents are preferably used when a two-phase reaction mixture is formed which can then be homogenized by the solvent. Suitable solvents are, for example, benzene, toluene, xylene, tert. Butanol, isoamyl alcohol; Acetonitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, dioxane, 1,2-dirnethoxy-thane, etc. The solvents should be inert towards the reactants, ie not react with them. The acrylic and methacrylic acid or their salts are used in the reaction in stoichiometric amounts, but preferably in excess, for example 1.1 to 10 molar. The reaction can be carried out in a wide temperature range, for example from 20 to 120 ^° C. However, the range from about 60 to 110 ^° C. is preferred.

If the perfluoroalkylglycols and anhydrides of acrylic or methacrylic acid are used, the reaction can also be carried out under the specified conditions, the reactants, for example, in stoichiometric ratios, at temperatures from 60 to 110 ^° C. and optionally in the presence of polymerization inhibitors Reaction brings.

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The inventive fluorinated acrylic acid esters can be homo- or due to their vinyl grouping in the molecule copolymerized with other ethylenically unsaturated copolymerizable compounds.

Homopolymers therefore contain repeating units of the formula

(12) R-CH-CH-OCCR ₁

OH R ₂ 0 CH ₂

wherein R is a perfluorinated aliphatic hydrocarbon radical having 3 to 22 carbon atoms and R ₁ and R _{2 are} hydrogen or methyl.

Those homopolymers which recurring units of the formulas

(13) CF _0. , CH-CH-OCCR ₁

η 2n + l | , Hi

OH R ₀ 0 CH ₀

(14) CF ₀ , -CH-CH-OCCR ₁ η, 2η _Ί +1, ι H ι

- OH R 0 CH

OH- R ₀ 0 CH ₀

* I ²

contain, in which R, and R _{2 have} the meaning given and η and n, integers from 4 to 14 bzt ^. 6 to 12 are.

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In addition to the units indicated for the homopolymers, the copolymers contain repeating units of other ethylenically unsaturated copolymerizable compounds.

The number of repeating units can be around 10 to 400.

The polymerization of the monomeric fluorinated acrylic acid esters can, for example, in solution or in emulsion, in the presence of free radical forming catalysts with themselves, with another fluorinated acrylic ester according to the invention or with other polymerizable compounds to form linear polymers.

For copolymerizing with the perfluoroalkyl monocarboxylic acid esters are suitable for example

a) vinyl esters of organic carboxylic acids, e.g. vinyl acetate, vinyl formate, vinyl butyrate, vinyl benzoate,

b) vinyl alkyl ketones and vinyl alkyl ethers such as vinyl methyl ketone and vinyl butyl ether,

c) vinyl halides, such as vinyl chloride, vinyl fluoride, vinylidene chloride,

d) vinyl pyrrolidone

e) vinyl aryl compounds such as styrene and substituted styrenes,

f) Derivatives of the acrylic acid series such as acrylonitrile or the acrylic acid amide and preferably its amide

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nitrogen-substituted derivatives, such as N-methylol

v
acrylamide, N-methylolacrylamide alkyl ether, N, N-dihydroxy ~

ethylacrylamide, N-tert.-butylacrylamide and hexamethylolmelamine triacrylamide, as well as the corresponding quaternized compounds5

-g) esters of the acrylic acid series, such as esters of acrylic acid,

Methacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid and mono- or di-alcohols with 1 to 18 carbon atoms or phenols, for example
Ethyl acrylate, glyeldyl acrylate, butyl acrylate, acrylic acid monoglycol ester _s dodecyl acrylate or N-dialkylaminoethyl methacrylate and the corresponding quaternized compound and

h) polymerizable olefins such as isobutylene, butadiene or
2-chlorobutadiene.

Preference is given to using esters, amides or methylol

amides of acrylic or methacrylic acid, V7ie aerylic acid ethyl

esters, butyl acrylate, glycidyl acrylate, glycol non-acrylate, calcium acrylate, acrylamide, methacrylate,
Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolacrylamide methyl ether, N-tert-butyl acrylamide, vinyl esters of organic carboxylic acids such as vinyl acetate; Styrene, vinyl halides such as vinyl chloride or vinylidene chloride; or polymerizable olefins such as isobutylene.

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The polymers are typically from 5 to 100, preferably from 40 to 98, percent by weight of a fluorinated one Acrylic acid ester and composed of 95 to 0, preferably 60 to 2% by weight of another compound. Particularly Such bi-, ter- and quaterpolymers have interesting technical properties, which in addition to AO up to 98 percent by weight of the monomeric fluorinated acrylic acid ester, based on the total weight of the monomers, is a reactive one Monomer, such as N-methylolacrylamide, an acrylic acid ester, such as Decyl acrylate and optionally a vinyl ester such as vinyl acetate.

The production of the polymers by homopolymerization or copolymerization of fluorinated acrylic acid esters Ethylenically copolymerizable with one or more other copolymers unsaturated monomers is carried out by customary methods, e.g. by block polymerization, bead polymerization, polymerization In aqueous emulsion or preferably by solvent polymerization in an organic solvent suitable for this purpose, such as acetone, benzene, sym.-dichloroethane, Ethyl acetate or trifluoromethyl benzene.

The polymerization is expediently carried out with heating, preferably to the boiling point of the solvent and with the addition of peroxidic or other, free Free radical-forming catalysts that dissolve in the reaction medium

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are borrowed, such as benzoyl peroxide, lauroyl peroxide, a, a .'- azo-, isobutyrodinitrile or potassium peroxydisulphate or redox systems such as potassium peroxydisulphate / sodium bisulphite or ferrous sulphate.

Depending on the type of polymerization conditions and the monomeric starting materials used, the polymeric Compounds in the form of viscous solutions, granules or obtained in the form of emulsions.

It is also possible to carry out the polymerization of the monomeric compounds in the presence of substrates. It can be done e.g. on glass fiber fabric or textile material. In this case, the substrate in question expediently with solutions or emulsions of the monomers impregnated and then the polymerization with additive a polymerization catalyst is effected by heating the material.

The preferred polymerization methods are emulsion polymerization in an aqueous medium and Solution polymerization.

The polymerization is preferably carried out within such a reaction time as is set is that a practically quantitative conversion of the monomer to the polymer is achieved. The optimal response time depends of the catalyst used and the polymerization temperature

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door and other conditions, but generally lies in the range of 0.5 to 24 hours.

The polymerization temperature in turn depends on the catalyst chosen. In the case of emulsion polymerization in aqueous media, it is generally in the range from 20 to 90 ^° C. Wherever possible, the polymerization is carried out at atmospheric pressure.

In emulsion polymerization, the monomer or monomers to be polymerized are polymerized together in an aqueous solution of an emulsifying agent under nitrogen to a given monomer concentration of about 5 to 50%. The temperature is usually increased to 40 to 70 ^° C. in order to bring about the polymerization in the presence of an added catalyst. The catalyst can be any of those commonly known for initiating polymerization of an ethylenically unsaturated compound. The concentration of the polymerization catalyst is usually between 0.1 and 2% based on the weight of the monomers.

Suitable emulsifiers are cationic, anionic or non-ionic surfactants. The hydrophobic Part of the emulsifier can be a hydrocarbon or a be fluorinated hydrocarbon.

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Suitable cationic emulsifying agents include, for example, quaternary ammonium salts or amine salts, the at least one long-chain alkyl, fluoroalkyl or an alkyl substituted benzene or naphthalene group for the delivery of the hydrophobic part.

Other suitable emulsifying agents are the nonionic surfactants, in which the hydrophilic Part of a Po Iy (äthojcy) group and the hydrophobic part of either a hydrocarbon, or a fluorocarbon group is like the ethylene oxide condensates of alkylphenols, Alkanols, alkylamines, alkylthiols, alkylcarboxylic acids, Fluoroalkyl carboxylic acids, fluoroalkylamides, and the like. Anionic emulsifiers are e.g. the sulfur r or phosphoric acid esters of the ethylene oxide condensates mentioned of long-chain alkylphenols, fatty alcohols and fatty amines.

In the solution polymerization, the monomer or monomers are dissolved in a suitable solvent, such as fluorinated solvents, for example hexafluoroxylene, benzotrifluoride or mixtures thereof with acetone and / or ethyl acetate and placed in a reaction vessel using initiators such as azobisisobutyronitrile or other azo initiators in concentrations of 0.1 to 2.0% ^{polymerized at 40 to 100 °} C. under nitrogen.

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Preferred solvents are hexafluoroxylene, benzotrifluoride, fluorine halogenated hydrocarbons, other fluorinated solvents and the like.

As mentioned at the outset, in addition to homopolymers, the polymerization of the new monomers can also valuable copolymers can be obtained with other ethylenically unsaturated monomers.

Another possibility of producing fluorine-containing copolymers (copolymers) is to use polymeric substances as obtained from the ethylenically unsaturated monomers or mixtures thereof, preferably e.g. polyacrylic or Polymethacrylic acid to react with perfluoroalkyl epoxides (e.g. of the formulas 8, 10 and 11), whereby polymers are obtained, in which the fluorinated side chain also has an ester bridge is bound.

The perfluoroalkyl carboxylic acid esters according to the invention can either as such, but preferably as homopolymers or copolymers for treatment, preferably for production oleophobic finishes used on porous or non-porous substrates. The porous substrates are leather, Paper and wood or, in particular, textile fiber materials. mentioned. Metal, plastic and glass surfaces are particularly suitable as non-porous substrates.

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The compounds according to the invention can be used further are used as wetting agents, emulsifiers, dispersants, leveling agents, foaming agents, dirt-repellent additives for Polishes and waxes or as additives for oils and lubricants against wear and corrosion.

As preferred textile materials which are treated with the monomeric or polymeric perfluoro compounds e.g. those made from native or regenerated cellulose, such as cotton, linen or rayon, Spun rayon or cellulose acetate, but also made of wool, synthetic polyamides, polyester or polyacrylonitrile into consideration. Mixed fabrics or mixed knitted fabrics made from cotton-polyester fibers can also advantageously be finished will. The textiles can be in the form of threads, fibers, flakes, fleeces, but preferably of woven fabrics or Knitted fabrics are available and are used, for example, as items of clothing, upholstery, decorative fabrics and carpets.

Preparations containing the monomeric or polymeric Perfluoro compounds can contain in the usual, per se be applied to the substrate in a known manner.

For oleophobic treatment, the substrates can be mixed with solutions, such as dispersions or emulsions of the monomeric or polymeric perfluorocompounds are treated. The monomers

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can e.g. be applied to the textile material from a solution in an organic solvent and after Thermally fix the evaporation of the solvent on the tissue. Polymers can also be made from suitable solvents apply to the tissues.

Fabrics can be impregnated, for example, by the exhaust process or on a padder that is charged with the preparation at room temperature. The impregnated material is then ^{dried at from 60 to 120 °} C. and then optionally subjected to a heat treatment above 100 ^° C., for example from 120 to 200 ^° C., advantageously in the presence of known acid-donating catalysts.

Further application methods are e.g. spraying, Brushing, rolling, dusting with subsequent heat setting or the transfer of the inventive Monomers or polymers from an auxiliary material (paper, film) under the influence of heat. The compounds according to the invention are applied in amounts of 0.1 to 10, preferably 0.5 to 5 percent by weight, based on the substrate.

At the same time as the compounds according to the invention, further agents can also be applied to the substrates e.g. wetting agents, softeners, water repellants, resin finishes or anti-crease agents.

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In addition to the oil-repellent effect that is achieved with the compounds according to the invention, one can particularly also so-called "soil release" on textile fiber substrates and achieve "antisoiling" effects: Of the polymerization products according to the invention, the copolymers are particularly suitable for this.

In the following examples, the present Invention further explained, but without restricting it to the scope of these examples. If nothing else is indicated, the parts are parts by weight and the percentages are percentages by weight.

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Examples

A. Preparation of the fluorinated acrylic acid esters

1. a) 1.44 g of acrylic acid are dissolved in 3 ml of acetonitrile. To this are added, while cooling and stirring, 0.81 g of triethylamine, a small spatula tip of hydroquinone and 4.62 g of perfluorooctylethylene oxide. The reaction mixture is two-phase at room temperature, but quickly becomes single-phase when heated. It is heated under nitrogen atmosphere at reflux for 4 hours at 80 ^c C. After cooling to room temperature, diluted with 15 ml of chloroform and extracted successively with 15 ml In-sulfuric acid, 15 ml of 1 molar soda solution and 5 ml water. After drying over sodium sulfate, the organic phase is fractionally distilled. 4.1 g (78% of theory) of the compound of the formula are obtained

OH 0

IN

(101) F- <CF ₂ ) g-CH - CH ₂ - O - C - CH = CH ₂

Boiling point: 85-87 ° C / O, OOl Torr
Melting point: 38-39 ° C

Analysis: found C 29.5 H 1.3 H (active) 0.20 calculated C 29.2 H 1.3 H (active) 0.19

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b) The procedure is as under a), but 4 ml of benzene are used as solvent and the reaction is allowed to react ^{at 80 ° C. for 10 hours.} 3.4 g (63% of theory) are obtained.

c) 0.81 g of triethylamine are dissolved in 7.20 g of acrylic acid with cooling. A small spatula tip of hydroquinone and 4.62 g of perfluorooctylethylene oxide are added. The reaction mixture is single phase at room temperature. ^{It is heated to 80 °} C. for 4 hours under a nitrogen atmosphere.

After cooling to room temperature, 50 ml of benzene are added, then shaken successively with 25 ml 0.5N sulfuric acid, 120 ml 1 molar soda solution and then 3 times with 10 ml of water each time. After drying over sodium sulfate, it is obtained by fractional distillation 3.3 g (62% of theory) of the compound of the formula (101). Boiling point: 90-93 ° C / 0.001 Torr

2. 2g perfluorooctyl ethylene glycol and 0.58 g acrylic anhydride become hydroquinone after adding a small spatula tip stirred together under a nitrogen atmosphere at 100 ° C. for 1 hour. It is allowed to cool and stirred for 1 hour at room temperature with 5 ml of saturated sodium hydrogen carbonate solution. It is extracted with 10 ml of chloroform, the organic phase is washed neutral with water and dried

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them over sodium sulfate. Fractional distillation provides 1.2 g (54% of theory) of the compound of the formula (101) Boiling point: 85-88 ° C / O, OOl Torr.

3. 0.81 g of triethylamine are added to 2.15 g of methacrylic acid with cooling and stirring. It is a small spatula tip of hydroquinone monomethyl ether and 4.62 perfluorooctyl-ethylene oxide are added and heated under Stickstoffatmosph'äre 8 hours to 80 ⁰ C, the reaction mixture is quickly single phase.

Are then 50'ml benzene and shaken at 60 ⁰ C successively with 15 ml In-sulfuric acid, 25 ml of 1 molar Sodalb'sung and 25 ml of water. The solution is dried, likewise at 60 ^° C., over sodium sulfate. On cooling, 4.2 g (77% of theory) of the compound of the formula crystallize

OH 0 dl «

ΠΛΟ \ I Il I J

^VJ - ^{U }} F- (CF ₀ ^ o-CH - CH ₀ - 0 - C - C = CH ₀ ZoZ Z

the end. Then the compound obtained is made from benzene recrystallized or crystallized in a high vacuum.

Gas chromatographic purity 100%.

Melting point: 64-65 ° C.

Analysis:

found C 30.9 H 1.6 H (active) 0.19 calculated C 30.7 H 1.6 H (active) 0.18

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4. 17.6 g of triethylamine are added slowly with cooling and stirring

added to 44.6g methacrylic acid. A spatula tip is given Hydroquinone and 100 g perfluoroalkyl-ethylene oxide homolog mixture

/ V

(103) F-f CF ^ -CH-CH ₂
m = 6, 8 "10 °

and stir for 8 hours under a nitrogen atmosphere at 80 ° C. After cooling, it is mixed with 300 ml of chloroform and shaken out successively with 200 ml of ln sulfuric acid, 600 ml. 1 molar soda solution and 100 ml of water and dried over sodium sulfate. Fractional distillation gives '98.5 g (83 % of theory) of the homolog mixture of the formula

OH 0

ΠΩ4Λ 'Ii ι J

■> ■ '■■ F- (CF ₂ - ^ - CH - CH ₂ - 0 - C - C = CH ₂

ra = 6, 8, 10

Boiling range: 72-95 ⁰ CyO ₁ OOl Torr. The product solidifies like a wax on storage.

5. a) 0.86 g of polyacrylic acid and 0.40 g of triethylamine are dissolved in a mixture of 10 ml dimethylformamide and 0.5 ml of water at 60 ⁰ C. One gives 4.62 g Perfluoralky1-ethylene oxide homologs mixture of the formula (103) are added and stirred for 1 hour at 100 ⁰ C, the reaction rate is thereby

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mixed homogeneous.

After cooling, the reaction mixture is poured into a mixture of 200 ml while stirring with a high-speed stirrer Water and 5 ml of 2N sulfuric acid. The failing one The precipitate is filtered off, washed and dried; 4.15 g (76%) of solid product are obtained. From the analytically determined F content of 55.4% found that about 59% of the carboxyl groups of the polyacrylic acid have been esterified by perfluoroalkyl ethylene oxide are.

b) 1.44 g of polyacrylic acid and 1.01 g of triethylamine are dissolved in a mixture of 10 ml of dimethylformamide and 0.5 ml of water. One gives 4.62 g perfluoroalkyl ethylene oxide homologs mixture of the formula (103) are added and stirred for 8 hours at reflux condenser at 100 ⁰ C to give a homogeneous solution. It is allowed to cool, diluted with 40 ml of methanol and slowly poured into a mixture of 200 ml of water and 10 ml of 2N sulfuric acid with stirring. A precipitate separates out and hardens after storage under water for one day. It then becomes a filter under water with the high-speed stirrer. crushed precipitate. After filtering off, washing and drying, 4.2 g (69% of theory) of a solid product are obtained; from the analytically determined F content

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of 49.17ο it results that approx. 37% of the carboxyl groups the polyacrylic acid esterified by berfluoroalkyl ethylene oxide have been.

c) 3.60 g of polyacrylic acid and 1.01 g of triethylamine are dissolved in a mixture of 20 ml of dimethylformamide and 0.5 ml of water. 4.62 g of perfluoroalkyl-ethylene oxide homolog mixture of the formula (103) are added and the mixture is stirred. Hours at 100 ⁰ C at Pvückfluss cooler to form a homogeneous solution is formed.

It is allowed to cool, diluted with 40 ml of methanol and poured into a mixture of 300 ml of water and 20 ml of 2N sulfuric acid with stirring. A strongly swollen precipitate separates out, which is isolated by filtration, washed well with water and dried. 7.3 g (89% of theory) of solid substance are obtained; from the analytically determined fluorine content of 37.8%, resulting in that approximately 187 _O have been esterified the carboxyl groups of the polyacrylic acid-ethylene oxide durch'Perfluoralkyl.

B. Preparation of the Polymers

6. A mixture of 30 parts of water, 0.6 parts of dodecyltri- * methylammonium chloride, 0.6 parts octadecyltrimethylr ammonium chloride, 0.4 part of vinyl acetate, 0.4 part of N-methylolacrylic acid amide, 5 parts of acetone and 9.2 parts of the

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Compound of the formula (104) is heated ^{to 70 ° C. with stirring and under a nitrogen atmosphere.} After adding a solution of 0.025 parts of potassium peroxydisulfate in 2.5 parts of water, the polymerization begins. 20 minutes later, another solution of 0.025 parts of potassium peroxydisulfate in 2.5 parts of water is added. ^{The resulting emulsion is kept at 70 °} C. for 3 hours to complete the polymerization. After cooling to room temperature, small amounts of precipitated products are filtered off.

About 51 parts of a finely dispersed emulsion with a resin content of 19% are obtained, corresponding to a yield of about 100%.

7. A mixture of 25 parts of water, 0.6 part of octadecyltrimethylammonium chloride, 0.6 part of dodecyltrimethylammonium chloride, 4.8 parts of heptyl methacrylate, 0.2 part of N-methylolacrylic acid amide, 5 parts of acetone and 5 parts of the compound of formula (104) is under and heated with stirring under a nitrogen atmosphere at 7O ⁰ C. After adding a solution of 0.007 parts of sodium metabisulphite in 1.2 parts of water and a solution of 0.025. Parts of potassium peroxydisulfate in 2.5 parts of water start the polymerization. 20 minutes later, a solution of 0.007 parts of sodium metabisulfite in 1.2

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Parts of water and a solution of 0.025 parts of potassium peroxydisulfate in 2.5 parts of water are added. The resulting emulsion is kept at 70 ° C. for 3 hours to complete the polymerization. After cooling to room temperature, small amounts of precipitated products are filtered off. You get about 48 parts of a
finely dispersed emulsion with a resin content of 23%,
corresponding to a yield of about 100%.

8. A mixture of 25 parts of water, 0.6 part of dodecyltrimethylammonium chloride, 0.6 part of octadecyltrimethylammonium chloride, 4.8 parts of hexyl methacrylate, 0.2
• Parts of N-methylolacrylic acid amide, 5 parts of acetone and 5 parts of the compound of the formula (101) are heated ^{to 70 ° C. with stirring and under a nitrogen atmosphere.} After the addition of a solution of 0.007 part of sodium metabisulphate in 1.2 parts of water and a solution of 0.025 part of potassium peroxydisulphate in 2.5 parts of water, the polymerization begins. 20. Minutes later, another solution of 0.007 part of sodium metabisulphite in 1.2 parts of water and a solution of 0.025 part of potassium peroxydisulphate in 2.5 parts of water are added. The corresponding - "avowed emulsion is held for 3 hours at 70 ⁰ C to complete the polymerization After cooling to.

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Small amounts of precipitated material are filtered off at room temperature Products. About 46 parts of a finely dispersed emulsion with a resin content of 23%, corresponding to one, are obtained 98% yield.

C. Application of the monomers and polymers

1. a) Cotton fabric is treated with a 5% solution in chloroform treated the monomeric ester mixture of formula (104), squeezed off and allowed to dry. Treated like that Fabric shows an oil repellency value of 100 (3-M test).

b) Cotton and wool fabrics are made with Q percent solutions the polymeric esters of Examples 5a) - c) treated in 95% aqueous acetone, squeezed off and dried at room temperature. The fabrics treated in this way show the following oil-repellent effects after the 3M test:

Table 1

Product of the example grade cotton 5 a) 5 b) 5 c) Q % Wool 1 0.5 1 100 110 120 130 140 140

(3M test: rejection values from 0 to 150, with 150 being the indicates best oil repellency)

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- ■ 27 -

2. Cotton fabrics and fabrics made of polyester-cotton (65/35) are impregnated with the polymer emulsions. The amount of fluorine applied is 0.1 or 0.2 percent by weight, based on the weight of the substrate. The impregnation preparations also contain 50 parts of a precondensate or reactant as used for the anti-crease finish, 30 parts of an extender customary for fluorochemicals and 8 parts per liter of magnesium chloride hexahydrate. The impregnated fabric is air dried and heat set 4 1/2 hours at 150 ⁰ C.

The finished fabrics are tested for their oil repellency according to the test method 118-1966 T of the American Association of Textile Chemists and Colourists (AATCC). The rejection values are between 0 and 8, with 8 indicating the best rejection value. The resistance of the ^{finish is tested by washing at 60 °} C. with a commercially available mild detergent.
Application liquor of the polymers:
15-70 parts of 15% strength emulsion of the polymers from 50 parts of an aqueous preparation (50% strength)

1 mole of hexamethylolmelamine hexamethyl ether and 1 mole of dimethylolethylene urea

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30 parts of a mixture of 50 parts paraffin

and 50 parts of a fatty acid amine conversion product (C, "fatty acid - triethanolamine) (Extender)

8 parts magnesium chloride hexahydrate 897-842 parts water.

The values obtained for the oil repellency are given in the tables below.

Table 2

Pol3 ^r mer according to
Regulation Fluorine amount% by weight
(on the fabric) Oil repellency on cotton fabric after 1 wash 6th
7th
8th 0.1
0.2
0.1
0.2
0.1
0.2 without laundry 3
4th
3
4th
5
5 3
5
3
4th
5-6
5-6

Table 3

Polymer according to
Regulation Fluorine amount% by weight
(on the fabric) 40988 Oil repellent on cotton poly
ester fabric after 1 wash 6th
7th
8th without laundry 2
2
2
3
4th
5 0.1
0.2
0.1
0.2
0.1
0.2 2
2
2
3
4th
4th 4/1298

Claims (20)

Claims ^ l J polymerization products from at least one fluorinated acrylic acid ester of the formula R - CH - CH - OC - C = CH ₀ ι I »II ² OH R ₂ 0 wherein R is a perfluorinated aliphatic hydrocarbon radical with 3 to 22 carbon atoms and R, and Rj Is hydrogen or methyl and optionally other copolymerizable ethylenically unsaturated monomers Links. 2. Homopolymers according to claim 1, characterized characterized in that they are repeating units of the formula R- CH - CH - OC - I.
CR i 1 Il I. OH R ₂ 0 CH ₀ contain, in which R is a perfluorinated aliphatic hydrocarbon residue with 3 to 22 carbon atoms and R, and R _{9 is} hydrogen or methyl. 409884/1298 3. Homopolymers according to claim 1, characterized in that the radical R is a straight-chain or branched perfluoroalkyl radical with 4 to 17 carbon atoms. 4. Homopolymers according to claim 3, characterized in that they contain recurring units of the formula CF ₀ ,, CH-CH-OC-CR ₁ η zn + 1 Ii {ι OH R ₀ 0 CH ₀ contain, in which R _{1 and R 2 are} hydrogen or methyl and η is an integer from 4 to 14. 5. Homopolymers according to claim 3, characterized in that they represent recurring units formula CF _n ., CH - CH - 0 - C - -C - R, ⁿ T ^η ι ^{± ι} ι ι Ii ι L. ' ^{L x} OH R ₉ 0 CH ₉ . ^Z I * contain, wherein R ,. and R _{9 is} hydrogen or methyl and n ^ is an integer from 6 to 12. 6. Copolymers according to claim 1, characterized in that they contain recurring units of the formula I R-CH- CH - OC - C - R, OH R ₀ 0 CH ₀ 409 884/1298 wherein R is a perfluorinated aliphatic hydrocarbon radical with 3 to 22 carbon atoms and R, and R ^ hydrogen or methyl and repeating units of at least one other ethylenically unsaturated, monomeric compound contain. 7. Copolymers according to claim 6, characterized characterized in that the perfluorinated hydrocarbon radical a straight-chain or branched perfluoroalkyl radical with to 17 carbon atoms. 8. Copolymers according to claim 6, characterized in that they contain recurring units of the formula CF ₀ "CH - CH ₀ -0-CCR ₁ η 2n + lι ι 2 n ι -1 ■ · ■■■■■ OH R ₀ 0 CH ₀ where R ₁ and R _{0 are} hydrogen or methyl and η is an integer from 4 to 14. 9. Copolymers according to claim 6, characterized in that they contain recurring units of the formula CF ₀ , .. CH - CH - 0 - C - C - R ₁ '- - ⁿ i ²ⁿ i ⁺¹ ι ι «ι 1 ^{L L} OH R ₀ 0 CH ₀ contain, vzoriri R, and R ^ hydrogen or methyl and n-, is an integer from 6 to 12. 409884/1298 10. Copolymers according to any one of claims 6 to 9, characterized in that the comonomers Esters, amides or methylolamides of acrylic or methacrylic acid, Styrene, vinyl halides, vinyl esters of organic acids or polymerizable olefins are used. 11. A process for the preparation of polymerization products according to any one of claims 1 to 10, characterized in that characterized in that the fluorinated acrylic acid esters are copolymerizable with themselves or with others "Polymerizes ethylenically unsaturated monomeric compounds. 12. The method geraäss claim 11, characterized in that fluorinated acrylic acid esters of the formula R - CH - CH - 0 - C - C = CH ₀ ti ti 2 OH R ₂ 0 where R is a perfluorinated aliphatic hydrocarbon radical having 3 to 22 carbon atoms and R and R _{9 are} hydrogen or methyl. 13. The method according to claim 11, characterized in that that one fluorinated acrylic acid esters of the formula R - CH - CH - 0 - C - C = CH ₀ ii. η 2 OH R ₂ 0 0 9 8 8 4/1298 where R is a perfluorinated aliphatic hydrocarbon radical with 3 to 22 carbon atoms and R ₁ and R «is hydrogen or methyl, polymerized together with esters, amides or methylolamides of acrylic or methacrylic acid, styrene, vinyl halides, vinyl esters of organic acids or polymerizable olefins. 14. Process for the preparation of polymerization products according to claim 1, characterized in that that you can make polymers from ethylenically unsaturated monomers Compounds, preferably polyacrylic or polymethacrylic acid, with perfluoroalkyl epoxides of the formula. R - CH-CH-R ₀ \ / ² converts, wherein R is a per fluorinated aliphatic hydrocarbon Substance residue with 3 to 22 carbon atoms and R ^ Is hydrogen or methyl. . 15. The method according to any one of claims 11 to 13, characterized in that in an organic solvent or works in an aqueous emulsion and in the presence of free radical initiators. 16. Use of the polymerization products according to any one of claims 1 to 10 as surface-active auxiliaries. .- "'■' 409884/1298 17. Use according to claim 16, characterized characterized in that the compounds are used as wetting agents, dispersants, emulsifiers, leveling agents, foaming agents, dirt-repellent additives for polishes and waxes or used as an anti-corrosive agent. 18. Use of the polymerization products according to any one of claims 1 to 10 for treating, in particular for oleophobic treatment of porous or non-porous substrates. 19. Use according to claim 18, characterized in that that porous substrates, in particular textile fiber materials, are oleophobized. 20. Use according to claim 18, characterized in that non-porous substrates, in particular Glass, metal or plastic surfaces, oleophobic. 409884/1298