EP0177447A1 - Diperfluoroalkyl carbamyl acrylates and methacrylates - Google Patents

Diperfluoroalkyl carbamyl acrylates and methacrylates Download PDF

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EP0177447A1
EP0177447A1 EP85810436A EP85810436A EP0177447A1 EP 0177447 A1 EP0177447 A1 EP 0177447A1 EP 85810436 A EP85810436 A EP 85810436A EP 85810436 A EP85810436 A EP 85810436A EP 0177447 A1 EP0177447 A1 EP 0177447A1
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carbon atoms
alk
formula
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vinyl
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EP0177447B1 (en
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Robert A. Falk
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Novartis AG
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Ciba Geigy AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine

Definitions

  • the present invention relates to diperfluoroalkylcarbamyl acrylates and methacrylates, polymers thereof and their use for the hydrophobization and oleophobization of cellulose and natural and synthetic polyamide substrates.
  • the present invention thus relates to new diperfluoroalkylcarbamyl acrylates and methacrylates - and polymers thereof - of the formula
  • Another object of this invention is a process for the preparation of such acrylate and methacrylate monomers.
  • the compounds of the formula (1) are advantageously prepared by reacting a compound of the formula wherein R f , R 1 , X, Alk, Q and n have the meanings given above, with a bifunctional compound of the formula wherein R, and R, have the meanings given above, at a temperature between -20 ° C and 100 ° C, preferably 10 ° C to 50 ° C, optionally in the presence of an inert organic solvent such as petroleum ether, 1,1,2 -Trichlortrifluoetzhan, methyl ethyl ketone, toluene, 2-Aethoxyäthylacetat, hexafluorxylene.
  • an inert organic solvent such as petroleum ether, 1,1,2 -Trichlortrifluoetzhan, methyl ethyl ketone, toluene, 2-Aethoxyäthylacetat, hexafluorxylene.
  • This process can expediently be carried out in the presence or absence of a customary catalyst, such as a urethane catalyst, for example dibutyltin dilaurate and / or a tertiary amine including trialkylamines, dialkylaralkylamines, dialkylarylamines, N-alkylheterocyclic amines and aromatic-heterocyclic amines, such as triethylamine, N Perform dimethylbenzylamine, N, N-dimethylaniline, N-methylpiperidine or pyridine. Since the reaction takes place with addition, no by-products are formed to any significant extent, which simplifies cleaning and recovery. The reaction product can often be used without any cleaning of the desired product. Otherwise, the vinyl monomer can be purified by conventional crystallization methods and obtained by filtration and evaporation.
  • a customary catalyst such as a urethane catalyst, for example dibutyltin dilaurate and / or a tertiary
  • the starting materials of formula (3) are known from the prior art.
  • the monomers of formula (3) are described, for example, in U.S. Pat. Patents 2718516 and 2821544 and in J. Coatings Technology, Volume 55, (703), pp. 55-61 (1983).
  • Monomers of the formula (3) are preferred in which R is alkylene having 2 to 6 carbon atoms and R is hydrogen or methyl, and these include isocyanatoethyl acrylate, isocyanatoethyl methacrylate, isocyanatobutyl acrylate, isocyanatobutyl methacrylate, isocyanatohexyl acrylate and isocyanatohexyl methacrylate. Because of its easy copolymerization and accessibility, isocyanatoethyl methacrylate is preferred as the monomer.
  • the present ⁇ , ⁇ -unsaturated ester monomers of the formula (1) are very reactive and have a strong tendency to form homo- or copolymers.
  • the compounds of formula (2) are known and can be easily prepared from known compounds by conventional methods.
  • Such a reduction is conveniently and easily carried out by reacting stoichiometric amounts of this carboxylic acid with a metal hydride such as lithium aluminum hydride in the presence of an inert solvent such as diethyl ether or tetrahydrofuran, at a reaction temperature between about 0 ° C and about 80 ° C, preferably between about 20 ° C and 70 ° C, and recovery of the resulting alcohol by diluting the reaction mixture with water and two equivalents of alkali, separating the organic phase from the aqueous phase and evaporating the organic phase to obtain the alcohol.
  • a metal hydride such as lithium aluminum hydride
  • an inert solvent such as diethyl ether or tetrahydrofuran
  • the compounds of formula (2) can be prepared by reacting the corresponding halogen-substituted alkyl epoxide with two moles of R f -R 1 -XH, where R f and R have the meanings given above and X is -S-, according to the in Example 2 of U.S. Patent 3883596 operation.
  • the diperfluoroalkylthio alcohols described in US Pat. No. 4,158,672 can also be used as the starting material.
  • thioether alcohols of formula (2) can be converted into the corresponding sulfonic alcohols by selective oxidation of the thio moiety by reaction with a suitable oxidizing agent such as peracetic acid or methachloroperbenzoic acid using two moles of oxidizing agent per mole of thioether alcohol at about 40 ° to 100 ° C. in an inert solvent such as Convert acetic acid, neutralize the reaction product with an aqueous base and evaporate the insoluble sulfonic alcohol therefrom.
  • a suitable oxidizing agent such as peracetic acid or methachloroperbenzoic acid
  • an inert solvent such as Convert acetic acid
  • the polymerization of the R f -acrylate and R, -methacrylate monomers according to the invention is analogous to the polymerization of such monomers as described in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, pp. 1044-1047 (Georg Thieme Verlag, Stuttgart, 1961) or CE Schildknecht, Vinyl and Related Polymers, pp. 179-255 (John Wiley and Sons, Inc., New York 1952).
  • the polymerization can generally be carried out in bulk, in solution, in suspension or in emulsion. Solution and emulsion polymerization are preferred
  • the monomer (s) to be polymerized are emulsified together in an aqueous solution of a surfactant to a predetermined monomer concentration of about 5% to about 50%.
  • the temperature is usually raised to between 40 ° C and 70 ° C to effect the polymerization in the presence of a catalyst.
  • a suitable catalyst is any of the generally known agents for initiating the polymerization of an ethylenically unsaturated compound.
  • the concentration of the catalyst for the polymerization is usually between 0.1% and 2% based on the monomer weight.
  • Suitable surfactants or emulsifiers include cation-active, anion-active and non-ionogenic types. Since the cation-active and non-ionogenic types can be used in most textile treatment baths, they are preferred.
  • the hydrophobic part of the surfactant can consist of hydrocarbon or fluorinated hydrocarbon.
  • Suitable surfactants or emulsifiers include, for example, nonionic surfactants in which there is a poly (ethoxy) group as the hydrophilic group and either a hydrocarbon or fluorocarbon group as the hydrophobic part, such as e.g. the ethylene oxide condensates of alkylphenols, alkanols, alkylamines, alkylthiols, alkylcarboxylic acids, fluoroalkylcarboxylic acids and fluoroalkylamines.
  • nonionic surfactants in which there is a poly (ethoxy) group as the hydrophilic group and either a hydrocarbon or fluorocarbon group as the hydrophobic part, such as e.g. the ethylene oxide condensates of alkylphenols, alkanols, alkylamines, alkylthiols, alkylcarboxylic acids, fluoroalkylcarboxylic acids and fluoroalkylamines.
  • Suitable cation-active surfactants include quaternary ammonium salts or amine salts which contain at least one long-chain alkyl, fluoroalkyl or benzene or naphthalene group substituted by higher alkyl, which supplies the hydrophobic part.
  • the polymerization preferably proceeds for a reaction time that is adjusted to essentially obtain a quantitative conversion of the fluorinated monomer.
  • the optimum reaction time depends on the catalyst used and the polymerization temperature and other conditions, but is generally in the range from 0.5 to 24 hours.
  • the polymerization temperature depends on the chosen catalyst. In the case of emulsion polymerization in aqueous media, it is generally in the range from 20 ° C. to 90 ° C. As far as possible, the polymerization is generally carried out most conveniently and preferably at atmospheric pressure.
  • the monomer (s) are dissolved in a suitable solvent such as e.g. fluorinated solvents, for example hexafluonocylol, trifluorotoluene or their mixtures with acetone and / or ethyl acetate, and polymerized using initiators such as azobisisobutyronitrile or other azo initiators in concentrations of 0.1 to 2.0%, based on the monomer weight, in a reaction vessel 40-100 ° C under nitrogen.
  • a suitable solvent such as e.g. fluorinated solvents, for example hexafluonocylol, trifluorotoluene or their mixtures with acetone and / or ethyl acetate
  • initiators such as azobisisobutyronitrile or other azo initiators in concentrations of 0.1 to 2.0%, based on the monomer weight, in a reaction vessel 40-100 ° C under nitrogen.
  • the monomers of the formula (1) can be homopolymerized or copolymerized with conventional monomers. These can be hydrophilic or hydrophobic monomers or mixtures thereof.
  • the resulting polymers thus contain structural units of the formula wherein R f , R 1 , R 2 , R, X, Alk, Q and n have the meanings given above.
  • hydrophilic comonomers are expediently used. If both hydrophobic and oieophobic properties are desired, the conventional comonomers advantageously have a predominantly hydrophobic character in order to achieve optimal results.
  • the amount of monomers of the formula (1) used in the copolymerization with the conventional comonomers can vary within wide limits depending on the degree of oleophobization and optionally hydrophobization desired in the finished polymer equipment, at least about 0.1 percent by weight to 99.9 is expediently used Weight percent of at least one monomer of formula (1) per unit weight of the mixture of conventional comonomers and monomer of formula (1).
  • Comonomers which can be used to prepare copolymers of the new monomers of the formula (1) are, for example: ethylene, and chlorine, fluorine, amido and cyano derivatives of ethylene, such as vinyl chloride, vinylidene chloride, vinyl fluoride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and N.
  • Propylene, butylene and isobutylene are the preferred ⁇ -olefins for use as comonomers with the new fluoromonomers of formula (1), with straight-chain and branched ⁇ -olefins with up to 10 carbon atoms in the side chain being usable.
  • Vinyk monomers containing perfluorinated side chains can also be used as comonomers with some of the new monomers of the formula (1). Examples of such perfluorinated monomers are fluorinated alkyl groups containing Vinylester, which are disclosed in US patents 2592069 and 243614. 4 Other useful monomers are acrylates and methacrylates and their derivatives, such as those known from US Patents 2628958, 3256230, 2839513, 3282905, 3252932 and 3304278.
  • Such monomers act as crosslinking agents in the curing process and are generally used in amounts of 0.01% to 5%, preferably 0.1% to 2% by weight, based on the weight of the comonomers.
  • Such reactive monomers that can be used are acrylic acid, methacrylic acid, acrylamide, methacrytamide, N-methylolacrylamide, 2-hydroxyethyl methacrylate or acrylate, hydroxypropyl acrylate or methacrylate and t-butylaminoethyl methyl amide and glycidyl methacrylate.
  • N-methylolacrylamide and 2-hydroxyethyl methacrylate are preferred.
  • Coatings from the homopolymers and copolymers according to the invention can be prepared as solutions or aqueous emulsions and applied from these.
  • suitable solvents are fluorakanes, fluorochloroalkanes, fluoroalkyl-substituted aromatics, alkyl esters of perfluoroalkanoic acids, chlorinated alkanes or aromatics, aromatic hydrocarbons, ketones, esters and ethers.
  • Particularly useful solvents are fluorinated solvents and in particular ⁇ , ⁇ , ⁇ -trifluorotoluoi, also known as benzotrifluoride, hexafluoroxy and their mixtures with ethyl acetate or acetone.
  • the concentrations of the fluorinated polymers according to the invention in the solvent for producing coatings with effective are generally in the range from 0.01 to 10% and preferably 0.1 to 2.0% by weight. Mixtures of emulsions of the polymers according to the invention with mixed emulsions of other polymers and copolymers are particularly useful for textile finishes.
  • the polymers and copolymers are generally of the non-fluorinated type; however, as noted below, other fluorinated polymers and copolymers can be used if desired.
  • non-fluorinated polymers which can be used in such mixtures are, but are not limited to, polymers and copolymers of alkyl acrylates and alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, hexyl methacrylate and n-octyl methacrylate.
  • Poly-n-octyl methacrylate is particularly suitable as such a polymer.
  • the polymers disclosed here have desirable soil-repellent properties.
  • the relative effectiveness of the polymers is expediently determined by measuring the contact angle of such a polymer with respect to water, methylene iodide and hexadecane.
  • reaction mixture is cooled in an ice bath, the precipitate is filtered off, washed with cold hexane and dried, giving 2.98 g (88% of theory) of the compound of the formula obtained as a white crystalline solid with a melting point of 84 ° C.
  • NMR shows proton resonances at ⁇ 1.99, 3 C (CH,) CH, protons; ⁇ 2.94.8 (C 1 F 17 CH 2 CH 2 S) 2 protons; ⁇ 3.57.2 NHCH 2 CH 2 O 2 C protons; ⁇ 3.85, 3 COCH, protons; ⁇ 4.29.2 NHCH 2 CH 2 O 2 C protons; ⁇ 5.5, 1 S 2 C HC proton; ⁇ 5.69, 1 proton and ⁇ 6.19, 1 C (CH 2 ) CH 2 proton; ⁇ 7.00, 1 NH proton; ⁇ 7.13, 2 (CH) 2 protons and ⁇ 7.29, 1 CHC (OCH,) proton.
  • Analysis for C 35 H 25 F 34 NO 5 S 2 Calculated: C, 33.6; H, 2.0; N, 1.12; F, 51.7. Found: C, 34.1; H, 1.9; N, 1.3; F, 52.1.
  • Example 2 2- [2.3- (Bis-1.1.2.2-tetrahvdroperfluoalkylthio) -porpoyloxvcarbonyl] aminoethyl methacrylate
  • Example 4 Polymer of 4- [methenyl- (bis-1.1.2.2-tetrahydroperfluorodecylthio)] - 2-methoxyphenoxycarbonylamioethyl methacrylate
  • Polymer films are made on glass plates and these show the following contact angles (degrees):

Abstract

Es werden diperfluoralkylhaltige Acrylat- und Methacrylatderivate der Formel <IMAGE> worin Rf für Perfluoralkyl, omega-Hydroperfluoralkyl oder perfluoralkoxysubstituiertes Perfluoralkyl, R1 für Alkylen mit 1 bis 12 Kohlenstoffatomen, X für -S- oder -SO2-, Alk für Alkantriyl mit 1 bis 14 Kohlenstoffatomen, Q für gegebenenfalls durch Chlor, Brom, Alkyl mit 1 bis 6 Kohlenstoffatomen oder Alkoxy mit 1 bis 6 Kohlenstoffatomen substituiertes Phenylen, n für 0 oder 1, R2 für Alkylen mit 1 bis 12 Kohlenstoffatomen und R3 für Wasserstoff oder Methyl stehen, deren Herstellung und deren Verwendung als hydrophobierende und oleophobierende Ausrüstungen auf Cellulosesowie natürlichen und synthetischen Polyamidsubstraten offenbart.There are diperfluoroalkyl-containing acrylate and methacrylate derivatives of the formula <IMAGE> in which Rf for perfluoroalkyl, omega-hydroperfluoroalkyl or perfluoroalkoxy-substituted perfluoroalkyl, R1 for alkylene with 1 to 12 carbon atoms, X for -S- or -SO2-, alk for alkane triyl with 1 to 14 Carbon atoms, Q represents phenylene optionally substituted by chlorine, bromine, alkyl having 1 to 6 carbon atoms or alkoxy having 1 to 6 carbon atoms, n represents 0 or 1, R2 represents alkylene having 1 to 12 carbon atoms and R3 represents hydrogen or methyl, the preparation thereof and their use as hydrophobic and oleophobic finishes on cellulose as well as natural and synthetic polyamide substrates.

Description

Vorliegende Erfindung betrifft Diperfluoralkylcarbamylacrylate und -methacrylate, Polymere daraus sowie deren Verwendung zur Hydrophobierung und Oleophobierung von Cellulose- sowie natürlichen und synthetischen Polyamidsubstraten.The present invention relates to diperfluoroalkylcarbamyl acrylates and methacrylates, polymers thereof and their use for the hydrophobization and oleophobization of cellulose and natural and synthetic polyamide substrates.

Gegenstand vorliegender Erfindung sind somit neue Diperfluoralkylcarbamylacrylate und -methacrylate - und Polymere daraus - der FormelThe present invention thus relates to new diperfluoroalkylcarbamyl acrylates and methacrylates - and polymers thereof - of the formula

Figure imgb0001
worin Rf für Perfluoralkyl, omega-Hydroperfluoralkyl oder Perfluoralkoxy-perfluoralkyl, R, für Alkylen mit 1 bis 12 Kohlenstoffatomen, X für -S- oder -SO2-, Alk für Alkantriyl mit 1 bis 14 Kohlenstoffatomen, Q für gegebenenfalls durch Chlor, Brom, Alkyl mit 1 bis 6 Kohlenstoffatomen oder Alkoxy mit 1 bis 6 Kohlenstoffatomen substituiertes Phenylen, n für 0 oder 1, R, für Alkylen mit 1 bis 12 Kohlenstoffatomen und R, für Wasserstoff oder Methyl stehen.
Figure imgb0001
 wherein R f for perfluoroalkyl, omega-hydroperfluoroalkyl or perfluoroalkoxy-perfluoroalkyl, R, for alkylene with 1 to 12 carbon atoms, X for -S- or -SO 2 -, alk for alkanetriyl with 1 to 1 4 carbon atoms, Q for optionally by chlorine , Bromine, alkyl with 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms substituted phenylene, n for 0 or 1, R, for alkylene with 1 to 12 carbon atoms and R, for hydrogen or methyl.

Ein weiterer Gegenstand dieser Erfindung ist ein Verfahren zur Herstellung von solchen Acrylat- und Methacrylatmonomeren.Another object of this invention is a process for the preparation of such acrylate and methacrylate monomers.

Noch ein weiterer Gegenstand vorliegender Erfindung sind Zusammensetzungen und ein Verfahren zur Hydrophobierung und Oleophobierung von Cellulose- sowie natürlichen und synthetischen Polyamidsubstraten unter Verwendung solcher die Diperfluoralkylcarbamylacrylate und -methacrylate bzw. deren Polymere enthaltender Zusammensetzungen.Yet another object of the present invention are compositions and a process for the hydrophobization and oleophobicization of cellulose and natural and synthetic polyamide substrates using compositions containing the diperfluoroalkylcarbamylacrylates and methacrylates or their polymers.

Die Rf-Gruppe in den Verbindungen der Formel (1) enthält im allgemeinen 1 bis 18 Kohlenstoffatome, vorzugsweise 3 bis 12 Kohlenstoffatome und besonders bevorzugt 6 bis 12 Kohlenstoffatome. Die Rf-Gruppe kann geradkettig oder verzweigt sein. Solche Rf-Gruppen sind bevorzugt, die Perfluoralkylreste darstellen, wie die perfluorierten Derivate von Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl und Dodecyl sowie deren isomere, wobei ein Gemisch aus Perfluoralkylresten Rf besonders vorteilhaft ist.

  • R1 ist vorzugsweise Alkylen mit 2 bis 12 und besonders bevorzugt 2 bis 6 Kohlenstoffatomen, und ganz besonders bevorzugt bedeutet es Aethylen oder Propylen.
  • R, bedeutet vorzugsweise Alkylen mit 2 bis 6 Kohlen- . stoffatomen, besonders bevorzugt geradkettiges Alkylen mit 2 bis 6 Kohlenstoffatomen und ganz besonders bevorzugt Aethyten.
  • R, ist besonders bevorzugt Methyl.
  • X steht vorzugsweise für -S-.
  • Alk ist vorzugsweise Alkantriyl mit 1 bis 7 Kohlenstoffatomen, falls n 1 ist. Bei dieser Ausführungsform sind die Rf-R1-X-Gruppen zweckmässig an dasselbe Kohlenstoffatom wie der Phenylenteil gebunden. Bei einer anderen Ausführungsform bedeutet Alk vorzugsweise -CH2-CH-CH2-, worin die R f-R1-X-Gruppen an die -CH, Teile gebunden sind.
  • In einer weiteren Ausführungsform bedeutet Alk Alkantriyl mit 2 bis 14, vorzugsweise 2 bis 6 Kohlenstoffatomen, sind die Rf-R1-X-Gruppen an dasselbe Kohlenstoffatom gebunden und ist n null. Bei dieser Ausführungsform ist der Carbamatsauerstoff zweckmässig an ein anderes Kohlenstoffatom gebunden als jene Rf-R1-X-Gruppen.
  • In noch einer anderen Ausführungsform steht Alk für
  • Alkantriyl mit 3 bis 14 Kohlenstoffatomen und sind die Rf-R1-X-Gruppen an benachbarte Kohlenstoffatome gebunden.
  • Q bedeutet vorzugsweise gegebenenfalls methyl- oder methoxysubstituiertes Phenylen.
The R f group in the compounds of formula (1) generally contains 1 to 18 carbon atoms, preferably 3 to 12 carbon atoms and particularly preferably 6 to 12 carbon atoms. The R f group can be straight-chain or branched. Such R f groups are preferred which represent perfluoroalkyl radicals, such as the perfluorinated derivatives of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl and their isomers, a mixture of perfluoroalkyl radicals R f being particularly advantageous.
  • R 1 is preferably alkylene with 2 to 12 and particularly preferably 2 to 6 carbon atoms, and very particularly preferably it means ethylene or propylene.
  • R preferably denotes alkylene with 2 to 6 carbon atoms. Substance atoms, particularly preferably straight-chain alkylene with 2 to 6 carbon atoms and very particularly preferably ethytes.
  • R is particularly preferably methyl.
  • X preferably represents -S-.
  • Alk is preferably alkanetriyl having 1 to 7 carbon atoms if n is 1. In this embodiment, the R f -R 1 -X groups are expediently bound to the same carbon atom as the phenylene part. In another embodiment, Alk preferably denotes -CH 2 -CH-CH 2 -, in which the R f -R 1 -X groups are bonded to the -CH, parts.
  • In a further embodiment, alk is alkanetriyl having 2 to 14, preferably 2 to 6, carbon atoms, the R f -R 1 -X groups are bonded to the same carbon atom and n is zero. In this embodiment, the carbamate oxygen is expediently bound to a different carbon atom than those R f -R 1 -X groups.
  • In yet another embodiment, Alk is
  • Alkantriyl with 3 to 14 carbon atoms and the R f -R 1 -X groups are bonded to adjacent carbon atoms.
  • Q is preferably optionally methyl- or methoxy-substituted phenylene.

Die Verbindungen der Formel (1) stellt man zweckmässig durch Umsetzung einer Verbindung der Formel

Figure imgb0002
worin Rf, R1, X, Alk, Q und n die oben angegebenen Bedeutungen haben, mit einer bifunktionellen Verbindung der Formel
Figure imgb0003
 worin R, und R, die oben angegebenen Bedeutungen haben, bei einer Temperatur zwischen -20°C und 100°C, vorzugsweise 10°C bis 50°C, gegebenenfalls in Gegenwart eines inerten organischen Lösungsmittels wie z.B. Petroläther, 1,1,2-Trichlortrifluoräthan, Methyläthylketon, Toluol, 2-Aethoxyäthylacetat, Hexafluorxylol her. Zweckmässig lässt sich dieses Verfahren in Gegenwart oder Abwesenheit eines üblichen Katalysators, wie eines Urethankatalysators, z.B. Dibutylzinndilaurat und/oder eines tertiären Amins einschliesslich Trialkylaminen, Dialkylaralkylaminen, Dialkylarylaminen, N-Alkylheterocyclischen Aminen und aromatisch-heterocyclischen Aminen, wie z.B. Triäthylamin, N,N-Dimethylbenzylamin, N,N-Dimethylanilin, N-Methylpiperidin oder Pyridin durchführen. Da die Umsetzung unter Addition verläuft, entstehen keine Nebenprodukte in bedeutsamem Ausmass, wodurch sich die Reinigung und Gewinnung vereinfacht Häufig lässt sich das Reaktionsprodukt ohne irgendwelche Reinigung des gewünschten Produkts verwenden. Andemfalls kann man das Vinylmonomer nach herkömmlichen Kristallisationsmethoden reinigen und durch Filtrieren und Eindampfen gewinnen.The compounds of the formula (1) are advantageously prepared by reacting a compound of the formula
Figure imgb0002
 wherein R f , R 1 , X, Alk, Q and n have the meanings given above, with a bifunctional compound of the formula
Figure imgb0003
 wherein R, and R, have the meanings given above, at a temperature between -20 ° C and 100 ° C, preferably 10 ° C to 50 ° C, optionally in the presence of an inert organic solvent such as petroleum ether, 1,1,2 -Trichlortrifluoräthan, methyl ethyl ketone, toluene, 2-Aethoxyäthylacetat, hexafluorxylene. This process can expediently be carried out in the presence or absence of a customary catalyst, such as a urethane catalyst, for example dibutyltin dilaurate and / or a tertiary amine including trialkylamines, dialkylaralkylamines, dialkylarylamines, N-alkylheterocyclic amines and aromatic-heterocyclic amines, such as triethylamine, N Perform dimethylbenzylamine, N, N-dimethylaniline, N-methylpiperidine or pyridine. Since the reaction takes place with addition, no by-products are formed to any significant extent, which simplifies cleaning and recovery. The reaction product can often be used without any cleaning of the desired product. Otherwise, the vinyl monomer can be purified by conventional crystallization methods and obtained by filtration and evaporation.

Die Ausgangsstoffe der Formel (3) sind aus dem Stand der Technik bekannt Die Monomeren der Formel (3) sind beispielsweise in den U.S. Patenten 2718516 und 2821544 sowie in J. Coatings Technology, Band 55, (703), S. 55-61 (1983) beschrieben. Solche Monomere der Formel (3) werden bevorzugt, worin R, fur Alkylen mit 2 bis 6 Kohlenstoffatomen und R, für Wasserstoff oder Methyl stehen, und dazu gehören Isocyanatoäthyl-acrylat, Isocyanatoäthyl-methacrylat, Isocyanatobutyl-acrylat, Isocyanatobutyl-methacrylat, Isocyanatohexyl-acrylat und Isocyanatohexyl-methacrylat. Wegen seiner leichten Copolymerisation und Zugänglichkeit wird Isocyanatoäthyl-methacrylat als Monomer bevorzugt.The starting materials of formula (3) are known from the prior art. The monomers of formula (3) are described, for example, in U.S. Pat. Patents 2718516 and 2821544 and in J. Coatings Technology, Volume 55, (703), pp. 55-61 (1983). Monomers of the formula (3) are preferred in which R is alkylene having 2 to 6 carbon atoms and R is hydrogen or methyl, and these include isocyanatoethyl acrylate, isocyanatoethyl methacrylate, isocyanatobutyl acrylate, isocyanatobutyl methacrylate, isocyanatohexyl acrylate and isocyanatohexyl methacrylate. Because of its easy copolymerization and accessibility, isocyanatoethyl methacrylate is preferred as the monomer.

Die vorliegenden α,β-ungesättigten Estermonomeren der Formel (1) sind sehr reaktionsfähig und besitzen eine starke Tendenz zur Bildung von Homo- oder Copolymeren.The present α, β-unsaturated ester monomers of the formula (1) are very reactive and have a strong tendency to form homo- or copolymers.

Die Verbindungen der Formel (2) sind bekannt und lassen sich leicht nach herkömmlichen Verfahren aus bekannten Verbindungen herstellen.The compounds of formula (2) are known and can be easily prepared from known compounds by conventional methods.

So sind solche Verbindungen der Formel (2), worin Alk für Alkantriyl mit 1 bis 7 Kohlenstoffatomen und n für 1 stehen, beispielsweise im U.S. Patent 4429162 beschrieben und solche, worin Alk der Formel -CH2-CH-CH2- entspricht, im U.S. Patent 3883596 als Beispiel angegeben.Compounds of the formula (2) in which Alk is alkanetriyl having 1 to 7 carbon atoms and n is 1 are described, for example, in US Pat. No. 4,429,162 and those in which Alk corresponds to the formula -CH 2 -CH-CH 2 - in US Patent 3883596 given as an example.

Femer werden solche Verbindungen der Formel (2), worin Alk für Alkantriyl mit 2 bis 14 Kohlenstoffatomen steht, die R, -R1-X-Gruppen an dasselbe Kohlenstoffatom gebunden sind und n null ist, unter anderem durch Reduktion der in U.S. Patent 4239915 beschriebenen Monocarbonsäure zu den entsprachenden Alkoholen hergestellt. Eine solche Reduktion erfolgt zweckmässig und leicht durch Umsetzung stöchiometrischer Mengen dieser Carbonsäure mit einem Metallhydrid wie Lithiumaluminiumhydrid in Gegenwart eines inerten Lösungsmittels, wie Diäthyläther oder Tetrahydrofuran, bei einer Reaktionstemperatur zwischen etwa 0°C und etwa 80°C, vorzugsweise zwischen ungefähr 20°C und 70°C, und Gewinnung des entstandenen Alkohois durch Verdünnen des Reaktionsgemischs mit Wasser und zwei Aequivalenten Alkali, Abtrennung der organischen Phase von der wässrigen Phase und Eindampfen der organischen Phase, um den Alkohol zu erhalten.Furthermore, those compounds of the formula (2) in which Alk is alkanetriyl having 2 to 14 carbon atoms, the R, -R 1 -X groups are bonded to the same carbon atom and n is zero, inter alia by reducing that in US Pat. No. 4,239,915 Monocarboxylic acid described to the corresponding alcohols. Such a reduction is conveniently and easily carried out by reacting stoichiometric amounts of this carboxylic acid with a metal hydride such as lithium aluminum hydride in the presence of an inert solvent such as diethyl ether or tetrahydrofuran, at a reaction temperature between about 0 ° C and about 80 ° C, preferably between about 20 ° C and 70 ° C, and recovery of the resulting alcohol by diluting the reaction mixture with water and two equivalents of alkali, separating the organic phase from the aqueous phase and evaporating the organic phase to obtain the alcohol.

Andernfalls kann man die Verbindungen der Formel (2) durch Umsetzung des entsprechender halogensubstituierten Alkylepoxids mit zwei Mol Rf-R1-X-H herstellen, worin Rf und R, die oben angegebenen Bedeutungen haben und X für -S- steht, gemäss der in Beispiel 2 des U.S. Patents 3883596 angegebenen Arbeitsweise. Als Ausgangsstoff kann man dabei auch die im U.S. Patent 4158672 beschriebenen Diperfluoralkylthioalkohole einsetzen.Otherwise, the compounds of formula (2) can be prepared by reacting the corresponding halogen-substituted alkyl epoxide with two moles of R f -R 1 -XH, where R f and R have the meanings given above and X is -S-, according to the in Example 2 of U.S. Patent 3883596 operation. The diperfluoroalkylthio alcohols described in US Pat. No. 4,158,672 can also be used as the starting material.

Diese Thioätheralkohole der Formel (2) lassen sich in die entsprechenden Sulfonalkohole durch selektive Oxidation des Thioteils durch Reaktion mit einem geeigneten Oxydationsmittel wie Peressigsäure oder Methachlorperbenzoesäure unter Verwendung von zwei Mol Oxydationsmittel pro Mol Thioätheralkohol bei etwa 40° bis 100°C in einem inerten Lösungsmittel wie Essigsäure, Neutralisieren des Reaktionsprodukts mit einer wässrigen Base und Abdampfen des unlöslichen Sulfonalkohols daraus umwandeln.These thioether alcohols of formula (2) can be converted into the corresponding sulfonic alcohols by selective oxidation of the thio moiety by reaction with a suitable oxidizing agent such as peracetic acid or methachloroperbenzoic acid using two moles of oxidizing agent per mole of thioether alcohol at about 40 ° to 100 ° C. in an inert solvent such as Convert acetic acid, neutralize the reaction product with an aqueous base and evaporate the insoluble sulfonic alcohol therefrom.

Die Pooymerisation der erfindungsgemässen R f-Acrylat-und R, -Methacrylatmonomeren ist analog der Polymerisation solcher Monomerer, wie sie in Houben-Weyl, Methoden der Organischen Chemie, Band 14/1, S. 1044-1047 (Georg Thieme Verlag, Stuttgart, 1961) oder C.E. Schildknecht, Vinyl and Related Polymers [Vinyl- und verwandte Polymere], S. 179-255 (John Wiley and Sons, Inc., New York 1952) beschrieben sind.The polymerization of the R f -acrylate and R, -methacrylate monomers according to the invention is analogous to the polymerization of such monomers as described in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, pp. 1044-1047 (Georg Thieme Verlag, Stuttgart, 1961) or CE Schildknecht, Vinyl and Related Polymers, pp. 179-255 (John Wiley and Sons, Inc., New York 1952).

Die Polymerisation lässt sich allgemein in der Masse, in Lösung, in Suspension oder in Emulsion durchführen. Lösungs- und Emulsionspolymerisation werden bevorzugtThe polymerization can generally be carried out in bulk, in solution, in suspension or in emulsion. Solution and emulsion polymerization are preferred

Bei der Emulsionspolymerisation werden das bzw. die zu polymerisierende(n) Monomer(en) in einer wässrigen Lösung eines Tensids auf eine vorgegebene Monomerkonzentration von etwa 5% bis etwa 50% zusammenemulgiert. Die Temperatur wird üblicherweise auf zwischen 40°C und 70°C erhöht, um die Polymerisation in Gegenwart eines Katalysators zu bewirken. Als geeigneter Katalysator kommen sämtliche der allgemein bekannten Mittel zur Einleitung der Polymerisation einer äthylenisch ungesättigten Verbindung in Frage. Die Konzentration des Katalysators zur Polymerisation liegt üblicherweise zwischen 0,1% und 2% bezogen auf das Monomerengewicht.In the emulsion polymerization, the monomer (s) to be polymerized are emulsified together in an aqueous solution of a surfactant to a predetermined monomer concentration of about 5% to about 50%. The temperature is usually raised to between 40 ° C and 70 ° C to effect the polymerization in the presence of a catalyst. A suitable catalyst is any of the generally known agents for initiating the polymerization of an ethylenically unsaturated compound. The concentration of the catalyst for the polymerization is usually between 0.1% and 2% based on the monomer weight.

Zu geeigneten Tensiden oder Emulgatoren zählen kationen-aktive, anionen-aktive und nicht-ionogene Typen. Da die kationen-aktiven und nicht-ionogenen Typen in den meisten Textilbehandlungsbädem verwendbar sind, werden sie bevorzugt. Der hydrophobe Teil des Tensids kann aus Kohlenwasserstoff oder fluoriertem Kohlenwasserstoff bestehen.Suitable surfactants or emulsifiers include cation-active, anion-active and non-ionogenic types. Since the cation-active and non-ionogenic types can be used in most textile treatment baths, they are preferred. The hydrophobic part of the surfactant can consist of hydrocarbon or fluorinated hydrocarbon.

Zu geeigneten Tensiden bzw. Emulgatoren gehören beispielsweise nicht-ionogene Tenside, bei denen als hydrophile Gruppe eine Poly-(äthoxy)-Gruppe und als hydrophober Teil entweder eine Kohlenwasserstoff- oder Fluorkohlenstoffgruppe vorliegen, wie z.B. die Aethylenoxydkondensate von Alkylphenolen, Alkanolen, Alkylaminen, Alkylthiolen, Alkylcarbonsäuren, Fluoralkylcarbonsäuren und Fluoralkylaminen.Suitable surfactants or emulsifiers include, for example, nonionic surfactants in which there is a poly (ethoxy) group as the hydrophilic group and either a hydrocarbon or fluorocarbon group as the hydrophobic part, such as e.g. the ethylene oxide condensates of alkylphenols, alkanols, alkylamines, alkylthiols, alkylcarboxylic acids, fluoroalkylcarboxylic acids and fluoroalkylamines.

Beispiele für geeignete kationen-aktive Tenside sind unter anderem quartäre Ammoniumsalze oder Aminsalze, die mindestens eine langkettige Alkyl-, Fluoralkyl- oder mit höherem Alkyl substituierte Benzol- oder Naphthalingruppe enthalten, die den hydrophoben Teil liefert.Examples of suitable cation-active surfactants include quaternary ammonium salts or amine salts which contain at least one long-chain alkyl, fluoroalkyl or benzene or naphthalene group substituted by higher alkyl, which supplies the hydrophobic part.

Die Polymerisation verläuft vorzugsweise für eine Reaktionszeit, die darauf eingestellt ist, im wesentlichen eine quantitative Umsetzung des fluorierten Monomeren zu erhalten. Die optimale Reaktionszeit ist dabei vom verwendeten Katalysator und der Polymerisationstemperatur sowie anderen Bedingungen abhängig, liegt aber im allgemeinen im Bereich von 0,5 bis 24 Stunden.The polymerization preferably proceeds for a reaction time that is adjusted to essentially obtain a quantitative conversion of the fluorinated monomer. The optimum reaction time depends on the catalyst used and the polymerization temperature and other conditions, but is generally in the range from 0.5 to 24 hours.

Die Polymerisationstemperatur hängt dabei vom gewählten Katalysator ab. Bei der Emulsionspolymerisation in wässrigen Medien liegt sie im allgemeinen im Bereich von 20°C bis 90°C. So weit möglich wird die Polymerisation allgemein am zweckmässigsten und vorzugsweise bei Atmosphärendruck durchgeführt.The polymerization temperature depends on the chosen catalyst. In the case of emulsion polymerization in aqueous media, it is generally in the range from 20 ° C. to 90 ° C. As far as possible, the polymerization is generally carried out most conveniently and preferably at atmospheric pressure.

Bei der Lösungspolymerisation löst man das bzw. die Monomere(n) in einem geeigneten Lösungsmittel wie z.B. fluorierten Lösungsmitteln, zum Beispiel Hexafluoncylol, Trifluortoluol oder deren Gemischen mit Aceton und/oder Essigester, und polymerisiert unter Verwendung von Initiatoren wie Azobisisobutyronitril oder anderen Azoinitiatoren in Konzentrationen von 0,1 bis 2,0%, bezogen auf das Monomerengewicht, in einem Reaktionsgefäss bei 40-100°C unter Stickstoff.In solution polymerization, the monomer (s) are dissolved in a suitable solvent such as e.g. fluorinated solvents, for example hexafluonocylol, trifluorotoluene or their mixtures with acetone and / or ethyl acetate, and polymerized using initiators such as azobisisobutyronitrile or other azo initiators in concentrations of 0.1 to 2.0%, based on the monomer weight, in a reaction vessel 40-100 ° C under nitrogen.

Die Monomeren der Formel (1) lassen sich homopolymerisieren oder mit herkömmlichen Monomeren copolymerisieren. Bei diesen kann es sich um hydrophile oder hydrophobe Monomere oder Gemische solcher handeln. Die entstandenen Polymeren enthalten somit Struktureinheiten der Formel

Figure imgb0004
worin Rf, R1, R2, R, X, Alk, Q und n die oben angegebenen Bedeutungen haben. Um schmutzabweisende Eigenschaften auf Textilmaterialien zu erhalten, setzt man zweckmässig hydrophile Comonomere ein. Sind sowohl hydrophobe als auch oieophobe Eigenschaften erwünscht, so besitzen die herkömmlichen Comonomeren vorteilhafterweise vorwiegend hydrophoben Charakter, um optimale Ergebnisse zu erzielen. Während die Menge an in der Copoiymerisation mit den herkömmlichen Comonomeren verwendeten Monomeren der Formel (1) je nach dem in der fertigen Polymerenausrüstung erwünschten Oleophobierungs- und gegebenenfalls Hydrophobierungsgrad in weiten Grenzen schwanken kann, setzt man zweckmässig mindestens etwa 0,1 Gewichtsprozent bis 99,9 Gewichtsprozent mindestens eines Monomeren der Formel (1) pro Gewichtseinheit des Gemenges aus herkömmlichen Comonomeren und Monomer der Formel (1) ein.The monomers of the formula (1) can be homopolymerized or copolymerized with conventional monomers. These can be hydrophilic or hydrophobic monomers or mixtures thereof. The resulting polymers thus contain structural units of the formula
Figure imgb0004
 wherein R f , R 1 , R 2 , R, X, Alk, Q and n have the meanings given above. In order to obtain dirt-repellent properties on textile materials, hydrophilic comonomers are expediently used. If both hydrophobic and oieophobic properties are desired, the conventional comonomers advantageously have a predominantly hydrophobic character in order to achieve optimal results. While the amount of monomers of the formula (1) used in the copolymerization with the conventional comonomers can vary within wide limits depending on the degree of oleophobization and optionally hydrophobization desired in the finished polymer equipment, at least about 0.1 percent by weight to 99.9 is expediently used Weight percent of at least one monomer of formula (1) per unit weight of the mixture of conventional comonomers and monomer of formula (1).

Zur Herstellung von Copofymeren der neuen Monomeren der Formel (1) verwendbare Comonomere sind zum Beispiel: Aethyten, sowie Chlor-, Fluor-, Amido- und Cyanderivate des Aethylens, wie Vinylchlorid, Vinylidenchlorid, Vinyffluorid, Acrylnitril, Methacrylnitril, Acrylamid, Methacrylamid und N,N-Dimethylacrylamid, Tetrafluoräthylen und Hexafluorpropylen; Acrylatund Methacrylatmonomere, insbesondere solche mit 1 bis 18 Kohlenstaffatomen in den Estergruppen, wie n-Propylmethacrylat, 2-Methylcyclohexyl-methacrylat, Methylmethacrylat,t-Butylmethacrylat, n-Butylmethacrylat, Methylacrylat Aethylacrylat, Propylacrylat, Butylacrylat, 3-Methylpentylacrylat, Octylacrylat, Tetradecylacrylat, s-Butylacrylat, 2-Aethylhexylacrylat, 2-Methoxyàthytatxylat und Phenylacrylat; Diene, insbesondere 1,3-Butadien, Isopren und Chloropren, 2-Fluorbutadien, 1,1,3-Trifluorbutadien, 1,1 ,2,3-Tetrafluorbutadien, 1,1,2-Trifluor3,4-dichlorbutadien sowie Tri- und Pentafluorbutadien; Stickstoff-vinylmonomere wie Vinylpyridin, N-Vinylamide, Vinylsuccinimid, Vinylpyrrolidon, N-Vinylcarbazol, Styrol und verwandte Monomere, die leicht mit den neuen erfindungsgemässen Estern copolymerisieren, wie o-Methylstyrol, p-Methylstyrol, 3,4-Dimethylstyrol, m-Aethylstyrol und 2,5-Diäthylstyrol; Vinylester, z.B. Vinytacetat und Vinylester substituierter Säuren wie beispielsweise Vinylmethoxyacetat, Vinyltrimethylacetat, Vinylisobutyrat, Isopropenylbutyrat, Vinyliactat, Vinylcaprylat, Vinylpelargonat, Vinytmyristat, Vinyloleat und Vinyllinoleat; sowie Vinylester aromatischer Säuren wie Vinylbenzoat. Propylen, Butylen und Isobutylen sind die bevorzugten α-Olefine zur Verwendung als Comonomere mit den neuen Fluormonomeren der Formel (1), wobei geradkettige und verzweigte α-Olefine mit bis zu 10 Kohlenstoffatomen in der Seitenkette verwendbar sind. Als Comonomere mit einigen der neuen Monomeren der Formel (1) sind auch perfluorierte Seitenketten enthaltende Vinykmonomere verwendbar. Beispiele für solche perfluorierte Monomere sind fluorierte Alkylgruppen enthaltende Vinylester, die in U.S. Patenten 2592069 und 2436144 offenbart sind. Weitere nützliche Monomere sind Acrylate und Methacrylate sowie deren Derivate, wie solche, die aus U.S. Patenten 2628958, 3256230, 2839513, 3282905, 3252932 und 3304278 bekannt sind.Comonomers which can be used to prepare copolymers of the new monomers of the formula (1) are, for example: ethylene, and chlorine, fluorine, amido and cyano derivatives of ethylene, such as vinyl chloride, vinylidene chloride, vinyl fluoride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and N. , N-dimethylacrylamide, tetrafluoroethylene and hexafluoropropylene; Acrylate and methacrylate monomers, in particular those with 1 to 18 carbon atoms in the ester groups, such as n-propyl methacrylate, 2-methylcyclohexyl methacrylate, methyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 3-methyl pentyl acrylate, 3-methyl pentyl acrylate s-butyl acrylate, 2-ethylhexyl acrylate, 2-methoxyathytate xylate and phenyl acrylate; Dienes, in particular 1,3-butadiene, isoprene and chloroprene, 2-fluorobutadiene, 1,1,3-trifluorobutadiene, 1,1, 2,3-tetrafluorobutadiene, 1, 1 , 2-trifluoro3,4-dichlorobutadiene and tri- and Pentafluorobutadiene; Nitrogen vinyl monomers such as vinyl pyridine, N-vinyl amides, vinyl succinimide, vinyl pyrrolidone, N-vinyl carbazole, styrene and related monomers which easily copolymerize with the new esters according to the invention, such as o-methyl styrene, p-methyl styrene, 3,4-dimethyl styrene, m-ethyl styrene and 2,5-diethylstyrene; Vinyl esters, for example vinyl acetate and vinyl esters of substituted acids, for example vinyl methoxy acetate, vinyl trimethyl acetate, vinyl isobutyrate, isopropenyl butyrate, vinyl octate, vinyl caprylate, vinyl pelargonate, vinyl myristate, vinyl oleate and vinyl linoleate; and vinyl esters of aromatic acids such as vinyl benzoate. Propylene, butylene and isobutylene are the preferred α-olefins for use as comonomers with the new fluoromonomers of formula (1), with straight-chain and branched α-olefins with up to 10 carbon atoms in the side chain being usable. Vinyk monomers containing perfluorinated side chains can also be used as comonomers with some of the new monomers of the formula (1). Examples of such perfluorinated monomers are fluorinated alkyl groups containing Vinylester, which are disclosed in US patents 2592069 and 243614. 4 Other useful monomers are acrylates and methacrylates and their derivatives, such as those known from US Patents 2628958, 3256230, 2839513, 3282905, 3252932 and 3304278.

Wie erwähnt, kann es auch wünschenswert sein, eine geringe Menge anderer reaktionsfähiger Comonomerer mitzuverwenden, z.B. um die Eigenschaften der neuen, bei der Anwendung dieser Erfindung erhaltenen Textilausrüstungen beim Waschen und bei der chemischen Reinigung zu verbessern. Solche Monomere wirken als Vemetzungsmittel beim Härtungsvorgang und werden im allgemeinen in Mengen von 0.01% bis 5%, vorzugsweise 0,1 °!o bis 2 Gew.-%, bezogen auf das Gewicht der Comonomeren, eingesetzt.As mentioned, it may also be desirable to include a small amount of other reactive comonomer, e.g. to improve the properties of the new washing and dry cleaning textile equipment obtained by using this invention. Such monomers act as crosslinking agents in the curing process and are generally used in amounts of 0.01% to 5%, preferably 0.1% to 2% by weight, based on the weight of the comonomers.

Erläuternde Beispiele für solche mitverwendbare reaktionsfähige Monomere sind Acrylsäure, Methacrylsäure, Acrylamid, Methacrytamid, N-Methylolacrylamid, 2-Hydroxyäthylmethacrylat oder -acrylat, Hydroxypropylacrylat oder -methacrylat und t-Butylaminoäthylmethaaylat sowie Glycidylmethacrylat. Darunter sind N-Methylolacrylamid und 2-Hydroxyäthylmethacrylat bevorzugt.Illustrative examples of such reactive monomers that can be used are acrylic acid, methacrylic acid, acrylamide, methacrytamide, N-methylolacrylamide, 2-hydroxyethyl methacrylate or acrylate, hydroxypropyl acrylate or methacrylate and t-butylaminoethyl methyl amide and glycidyl methacrylate. Among them, N-methylolacrylamide and 2-hydroxyethyl methacrylate are preferred.

Beschichtungen aus den efindungsgemässen Homopolymeren und Copolymeren können als Lösungen oder wässrige Emulsionen hergestellt und aus diesen aufgebracht werden. Als Lösungsmittel eignen sich z.B. Fluorakane, Fluorchloralkane, fluoralkylsubstituierte Aromaten, Alkylester von Perfluoralkansäuren, chlorierte Alkane oder Aromaten, aromatische Kohlenwasserstoffe, Ketone, Ester und Aether. Besonders zweckmässige Lösungsmittel sind fluorierte Lösungsmittel und insbesondere α,α,α-Trifluortoluoi, auch als Benzotrifluorid bekannt, Hexafluorxyol und deren Gemische mit Essigester oder Aceton. Die Konzentrationen der erfindungsgemässen fluorierten Polymeren im Lösungsmittel zur Erzeugung von Ueberzügen mit wirksamen öl- und wasserabstossenden Eigenschaften liegen im allgemeinen im Bereich von 0,01 bis 10% und vorzugsweise 0,1 bis 2,0 Gew.-%. Gemische aus Emulsionen der erfindungsgemäsaen Polymeren mit verrmischten Emulsionen anderer Polymerer und Copolymerer sind besonders zweckmässig für Textilausrüstungen. Die Polymeren und Copolymeren gehören im allgemeinen dem nichtfluorierten Typ an; wie unten angegeben sind jedoch andere fluorierte Polymere und Copolymere gewünschtenfalls verwendbar. Beispiele für in sotchen Gemischen verwendbare nichtfluorierte Polymere sind, ohne darauf beschränkt zu sein, Polymere und Copolymere von Alkylacrylaten und Alkylmethacryulaten, wie Methylmenthacrylat, Aethylmetacrylat, Hexylmethacrylat und n-Octylmethacrylat. Poly-n-octylmethacrylat ist als solches Polymer besonders geeignet. Ferner kommen Polymere und Copolymere von Acrytsäure, Methacrylsäure, Styrol, Alkylstyrol, Butadien, 2-Methyl-1,3-butadien, 2-Chior-1,3-butadien, Polymere und Copolymere von Vinylestem wie Vinylacetat, Vinylbutyrat, Vinyllaurat, Vinylstearat und Vinyl-2-äthylhexanoat, Polymere und Copolymere von Vinylhalogeniden und Vinylidenhalogeniden, wie Vinylchlorid, Vinylidenchlorid, Vinylfluorid und Vinylidenfluorid, Polymere und Copolymere von Allylestem wie Allylpropionat oder Allylcaprylat, Polymere und Copolymere von Vinyläthem wie Methylvinyläther, Cetylvinyläther, sowie Polymere und Copolymere von Acrylamid, Methacrylamid, N-Methylolacrylamid, N-Methylolmethacrylamid, N-Isopropylacrylamid und Methacrylnitril dabei in Frage.Coatings from the homopolymers and copolymers according to the invention can be prepared as solutions or aqueous emulsions and applied from these. Examples of suitable solvents are fluorakanes, fluorochloroalkanes, fluoroalkyl-substituted aromatics, alkyl esters of perfluoroalkanoic acids, chlorinated alkanes or aromatics, aromatic hydrocarbons, ketones, esters and ethers. Particularly useful solvents are fluorinated solvents and in particular α, α, α-trifluorotoluoi, also known as benzotrifluoride, hexafluoroxy and their mixtures with ethyl acetate or acetone. The concentrations of the fluorinated polymers according to the invention in the solvent for producing coatings with effective The oil and water repellent properties are generally in the range from 0.01 to 10% and preferably 0.1 to 2.0% by weight. Mixtures of emulsions of the polymers according to the invention with mixed emulsions of other polymers and copolymers are particularly useful for textile finishes. The polymers and copolymers are generally of the non-fluorinated type; however, as noted below, other fluorinated polymers and copolymers can be used if desired. Examples of non-fluorinated polymers which can be used in such mixtures are, but are not limited to, polymers and copolymers of alkyl acrylates and alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, hexyl methacrylate and n-octyl methacrylate. Poly-n-octyl methacrylate is particularly suitable as such a polymer. In addition there are polymers and copolymers of acrylic acid, methacrylic acid, styrene, alkylstyrene, butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, polymers and copolymers of vinyl esters such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate and Vinyl-2-ethylhexanoate, polymers and copolymers of vinyl halides and vinylidene halides, such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride, polymers and copolymers of allyl esters such as allyl propionate or allyl caprylate, polymers and copolymers of vinyl ether such as methyl vinyl ether, acryl and vinyl amide copolymers, and cetyl vinyl ether, Methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-isopropylacrylamide and methacrylonitrile are possible.

Die hier offenbarten Polymeren besitzen wünschenswerte schmutzabweisende Eigenschaften. Die relative Wirksamkeit der Polymeren wird dabei zweckmässig durch Messungen des Kontaktwinkels eines solchen Polymeren gegenüber Wasser, Methylenjodid und Hexadecan festgestellt.The polymers disclosed here have desirable soil-repellent properties. The relative effectiveness of the polymers is expediently determined by measuring the contact angle of such a polymer with respect to water, methylene iodide and hexadecane.

Die nachfolgenden Beispiele dienen zur Erläuterung.The following examples serve to explain.

Beisoiel 4-[Methenyl-(bis-1.1.2.2-tetrahvdrooerfluordecvlthio)]-2-met- hoxy-phenoxvcwbonylamidoäthyl-methacrylaExample 4- [methenyl- (bis-1.1.2.2-tetrahvdrooerfluordecvlthio)] - 2-methoxy-phenoxvcwbonylamidoethyl-methacryla

Man bringt 3. g (2,742 mMol) 4-[Methenyl-(bis-1,1,2,2-tetrahydroperfluordecylthio)]-2-methoxyphenol (vgl. U.S. Patent 4429162) unter Stickstoff in 15 ml Hexan bei 50°C - 55°C 12 Stunden lang in Gegenwart katalytiscther Mengen Triäthylamin und Dibutylzinndilaurat mit 467 mg (3,016 mMol) 2-lsocyanatoäthyl-methacrylat zur Reaktion. Man kühlt das Reaktionsgemisch im Eisbad, filtriert den Niederschlag ab, wäscht diesen mit kaltem Hexan und trocknet, wobei man 2,98 g (88% der Theorie) der Verbindung der Formel

Figure imgb0005
als weissen kristallinen Feststoff vom Schmelzpunkt 84°C erhält NMR zeigt Protonenresonanzen bei δ 1,99, 3 C(CH,)CH, Protonen; δ 2,94, 8 ( C1F17CH2CH2S)2-Protonen; δ 3,57, 2 NHCH2CH2O2C-Protonen; δ 3,85, 3 COCH,-Protonen; δ 4,29, 2 NHCH2CH2O2C-Protonen; δ 5,5, 1 S2C H-C-Proton; δ 5,69, 1 Proton und δ 6,19, 1 C (CH2)CH2-Proton; δ 7,00, 1 NH-Proton; δ 7,13, 2 ( CH)2-Protonen und δ 7,29, 1 CHC(OCH,)-Proton. Analyse für C35H25F34NO5S2: Berechnet: C, 33,6; H, 2,0; N, 1,12; F, 51,7. Gefunden: C, 34,1; H, 1,9; N, 1,3; F, 52,1.3. g (2.742 mmol) of 4- [methenyl- (bis-1,1,2,2-tetrahydroperfluorodecylthio)] - 2-methoxyphenol (see US Pat. No. 4,429,162) are brought under nitrogen in 15 ml of hexane at 50 ° C. 55 ° C for 12 hours in the presence of catalytic amounts of triethylamine and dibutyltin dilaurate with 467 mg (3.016 mmol) of 2-isocyanatoethyl methacrylate for reaction. The reaction mixture is cooled in an ice bath, the precipitate is filtered off, washed with cold hexane and dried, giving 2.98 g (88% of theory) of the compound of the formula
Figure imgb0005
 obtained as a white crystalline solid with a melting point of 84 ° C. NMR shows proton resonances at δ 1.99, 3 C (CH,) CH, protons; δ 2.94.8 (C 1 F 17 CH 2 CH 2 S) 2 protons; δ 3.57.2 NHCH 2 CH 2 O 2 C protons; δ 3.85, 3 COCH, protons; δ 4.29.2 NHCH 2 CH 2 O 2 C protons; δ 5.5, 1 S 2 C HC proton; δ 5.69, 1 proton and δ 6.19, 1 C (CH 2 ) CH 2 proton; δ 7.00, 1 NH proton; δ 7.13, 2 (CH) 2 protons and δ 7.29, 1 CHC (OCH,) proton. Analysis for C 35 H 25 F 34 NO 5 S 2 : Calculated: C, 33.6; H, 2.0; N, 1.12; F, 51.7. Found: C, 34.1; H, 1.9; N, 1.3; F, 52.1.

Beispiel 2: 2-[2.3-(Bis-1.1.2.2-tetrahvdroperfluoalkylthio)-porpoyloxvcar- bonyl]-aminoäthyl-methacrylatExample 2: 2- [2.3- (Bis-1.1.2.2-tetrahvdroperfluoalkylthio) -porpoyloxvcarbonyl] aminoethyl methacrylate

Man bringt 10,0 g (21,85 mMol) 2,3-[Bis-1,1,2,2-tetrahydropefluoralkylthio)-1-propanol] (vgl. U.S. Patent 3883596) vom Durchschnittsmolekulargewicht 457,5 unter Stickstoff in 270 ml Hexan bei 50°-55°C 12 Stunden lang in Gegenwart einer katalytischen Menge Dibutylzinndilaurat mit 3,726 g (24 mMol) 2-Isocyanatoäthyl-methacrylat zur Reaktion. Man kühlt das Reaktionsgemisch im Eisbad, filtriert das Produkt ab, wäscht dieses mit kaltem Hexan und trocknet, wobei man 8,7 g (65,4% der Theorie) der Verbindung der Formel (200) RfCH2CH2SCH2CH(SCH2CH2R f)CH2O2CNHCH- 2CH2O2CC(CH2)=CH2 als weissen kristallinen Feststoff vom Schmelzpunkt 55-56°C erhält NMR zeigt Protonenresonanzen bei δ 1,93, 3 C(CH2)CH2-Protonen; δ 2,13-3,33, 10 R6CH2CH2SCH(CH2SCH2CH2R f)-Protonern, δ 3,47, 2 O2CNHCH2CH2-Protonen und 1 SCH(CH2SCH2CH2R f)-Proton; δ 4,23, 4 NHCH2CH2O2C- und CHCH2O2C-Protonen; δ 4,87, 1 NH-Proton; δ 5,55 und δ 6,11, 2 C(CH2)CH2-Protonen.10.0 g (21.85 mmol) of 2,3- [bis-1,1,2,2-tetrahydropefluoroalkylthio) -1-propanol] (see US Pat. No. 3,883,596) with an average molecular weight of 457.5 are brought into 270 in nitrogen ml of hexane at 50 ° -55 ° C for 12 hours in the presence of a catalytic amount of dibutyltin dilaurate with 3.726 g (24 mmol) of 2-isocyanatoethyl methacrylate for reaction. The reaction mixture is cooled in an ice bath, the product is filtered off, washed with cold hexane and dried, 8.7 g (65.4% of theory) of the compound of the formula (200) R f CH 2 CH 2 SCH 2 CH (SCH 2 CH 2 R f ) CH 2 O 2 CNHCH- 2 CH 2 O 2 CC (CH 2 ) = CH 2 obtained as a white crystalline solid with a melting point of 55-56 ° C. NMR shows proton resonances at δ 1.93, 3 C. (CH 2 ) CH 2 protons; δ 2.13-3.33, 10 R 6 CH 2 CH 2 SCH (CH 2 SCH 2 CH 2 R f ) protons, δ 3.47, 2 O 2 CNHCH 2 CH 2 protons and 1 SCH (CH 2 SCH 2 CH 2 R f ) proton; δ 4.23.4 NHCH 2 CH 2 O 2 C and CHCH 2 O 2 C protons; δ 4.87, 1 NH proton; δ 5.55 and δ 6.11, 2 C (CH 2 ) CH 2 protons.

Beispel 3: Polvmer des 2-[2.3-Bis-1.1.2.2-tetrahydroperfluoralkylthio)-propyloxycarbon- vll-aminoäthyl-methacrylatsExample 3: Polymer of 2- [2.3-bis-1.1.2.2-tetrahydroperfluoroalkylthio) propyloxycarbon-III-aminoethyl methacrylate

Man löst 3 g 2-[2,3-Bis-1,1,2,2-tetrahydroperfluoralkylthio)-propyloxycarb- onyl]-aminoäthyl-methacrylat und 0,1 g 1,1'-Azobis-(cyancycloexan) in 27 g Hexafluoncylol, spült mit Stickstoff, schmilzt im Vakuum in eine Ampulle ein und polymerisiert 12 Stunden lang bei 95°C im Rührbad. NMR zeigt keine Protonenresonanzen im Bereich δ 5-6,5.3 g of 2- [2,3-bis-1,1,2,2-tetrahydroperfluoroalkylthio) propyloxycarbonyl] aminoethyl methacrylate and 0.1 g of 1,1'-azobis (cyanocycloexane) are dissolved in 27 g Hexafluoncylol, flushed with nitrogen, melts into an ampoule in a vacuum and polymerizes for 12 hours at 95 ° C. in a stirred bath. NMR shows no proton resonances in the range δ 5-6.5.

Beispiel 4: Polymer des 4-[Methenyl-(bis-1.1.2.2-tetrahydroperfluordecylthio)]-2-met- hoxy-phenoxycarbonylamioäthyl-methacrylatsExample 4: Polymer of 4- [methenyl- (bis-1.1.2.2-tetrahydroperfluorodecylthio)] - 2-methoxyphenoxycarbonylamioethyl methacrylate

Man löst 1,5 g 4-[Methenyl-(bis-1,1,2,2-tertahydroperfluordecylthio)]-2-met- hoxy-phenoxycarbonylamlinoäthylmethacrylat und 0,075 g 1,1'-Azobis-(cyancyclohexan) in 13,5 g Hexafluorxylol, spült mit Stickstoff, schmilzt im Vakuum in einer Ampulle ein und polymerisiert 12 Stunden lang bei 95°C im Rührbad. NMR zeigt keine Protonenresonanzen im Bereich δ 5-6,5.1.5 g of 4- [methenyl- (bis-1,1,2,2-tertahydroperfluorodecylthio)] - 2-methoxyphenoxycarbonylamlinoethyl methacrylate and 0.075 g of 1,1'-azobis (cyanocyclohexane) are dissolved in 13.5 g of hexafluoroxylene, flushed with nitrogen, melts in a vial in vacuo and polymerizes for 12 hours at 95 ° C. in a stirred bath. NMR shows no proton resonances in the range δ 5-6.5.

Beispie) 5:Example 5:

Polymerfilme werden auf Glasplatten hergestellt, und diese zeigen die folgenden Kontaktwinkel (Grad):

Figure imgb0006
Polymer films are made on glass plates and these show the following contact angles (degrees):
Figure imgb0006

Claims (17)

1. Verbindungen der Formel
Figure imgb0007
worin Rf für Perfluoralkyl, omega-Hydroperfluoralkyl oder perfluoralkoxysubstituiertes Perfluoralkyl, R, für Alkylen mit 1 bis 12 Kohlenstoffatomen, X für -S- oder -SO2-, Alk für Alkantryl mit 1 bis 14 Kohlenstoffatomen, Q für gegebenenfalls durch Chlor, Brom, Alkyl mit 1 bis 6 Kohlenstoffatomen oder Alkoxy mit 1 bis 6 Kohlenstoffatomen substituiertes Phenylen, n für 0 oder 1, R, für Alkylen mit 1 bis 12 Kohlenstoffatomen und R, für Wasserstoff oder Methyl stehen.1. Compounds of the formula
Figure imgb0007
 wherein R f for perfluoroalkyl, omega-hydroperfluoroalkyl or perfluoroalkoxy-substituted perfluoroalkyl, R, for alkylene with 1 to 12 carbon atoms, X for -S- or -SO 2 -, alk for alkanetryl with 1 to 14 carbon atoms, Q for optionally by chlorine, bromine , Alkyl with 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms substituted phenylene, n for 0 or 1, R, for alkylene with 1 to 12 carbon atoms and R, for hydrogen or methyl. 2. Verbindungen nach Anspruch 1, dadurch gekennzeichnet, dass Rf 1 bis 18 Kohlenstoffatome enthält.2. Compounds according to claim 1, characterized in that R f contains 1 to 18 carbon atoms. 3. Verbindungen nach Anspruch 2, dadurch gekennzeichnet, dass als Rf Perfluoralkyl vorliegt3. Compounds according to claim 2, characterized in that the R f is perfluoroalkyl 4. Verbindungen nach Anspruch 3, dadurch gekennzeichnet, dass R, für Alkylen mit 2 bis 6 Kohlenstoffatomen steht4. Compounds according to claim 3, characterized in that R represents alkylene with 2 to 6 carbon atoms 5. Verbindungen nach Anspruch 4, dadurch gekennzeichnet, dass R, für Methyl steht5. Compounds according to claim 4, characterized in that R is methyl 6. Verbindungen nach Anspruch 1, dadurch gekennzeichnet, dass X für -S- steht6. Compounds according to claim 1, characterized in that X stands for -S- 7. Verbindungen nach Anspruch 3, dadurch gekennzeichnet, dass Alk für Alkantriyl mit 1 bis 7 Kohlenstoffatomen steht und n 1 ist.7. Compounds according to claim 3, characterized in that Alk is alkanetriyl having 1 to 7 carbon atoms and n is 1. 8. Verbindungen nach Anspruch 3, dadurch gekennzeichnet, dass Alk für -CH2-CH-CH2- steht, worin die Rf-R1-X-Gruppen an die -CH2-Teile gebunden sind.8. Compounds according to claim 3, characterized in that Alk is -CH 2 -CH-CH 2 -, wherein the R f -R 1 -X groups are bonded to the -CH 2 parts. 9. Verbindung nach Anspruch 3, worin Alk für Alkantriyl mit 2 bis 14 Kohlenstoffatomen steht, die Rf -R1-X-Gruppen an dasselbe Kohlenstoffatom gebunden sind und n null ist.9. A compound according to claim 3, wherein Alk is alkanetriyl having 2 to 14 carbon atoms, the R f -R 1 -X groups are bonded to the same carbon atom and n is zero. 10. Verbindungen nach Anspruch 3, dadurch gekennzeichnet, dass Alk für Alkantriyl mit 3 bis 14 Kohlenstoffatomen steht und die Rf R1-X-Gruppen an benachbarte Kohlenstoffatome gebunden sind.10. Compounds according to claim 3, characterized in that Alk is alkanetriyl having 3 to 14 carbon atoms and the R f R 1 -X groups are bonded to adjacent carbon atoms. 11. Verbindungen nach Anspruch 7, daduruch gekennzeichnet, dass X für -S- steht11. Compounds according to claim 7, characterized in that X stands for -S- 12. Polymere mit Struktureinheiten der Formel
Figure imgb0008
worin Rf, R1, R2, R3, X, Alk, Q und n die in Anspruch 1 angegebenen Bedeutungen haben.12. Polymers with structural units of the formula
Figure imgb0008
 wherein R f , R 1 , R 2 , R 3 , X, Alk, Q and n have the meanings given in claim 1. 13. Polymere nach Anspruch 12, dadurch gekennzeichnet, dass sie ein Homopolymer darstellen.13. Polymers according to claim 12, characterized in that they represent a homopolymer. 14. Polymere nach Anspruch 12, dadurch gekennzeichnet, dass sie ein Copolymer darstellen.14. Polymers according to claim 12, characterized in that they represent a copolymer. 15. Verfahren zur Hydrophobierung und Oleophobierung von Textilien, dadurch gekennzeichnet, dass man diese Textilien durch Behandlung mit einer Lösung oder einer wässrigen Emulsion eines Polymeren nach Anspruch 10 beschichtet15. A process for the hydrophobization and oleophobization of textiles, characterized in that these textiles are coated by treatment with a solution or an aqueous emulsion of a polymer according to claim 10 16. Verfahren zur Herstellung von Verbindungen der Formel (1), dadurch gekennzeichnet, dass man eine Verbindung der Formel16. A process for the preparation of compounds of formula (1), characterized in that a compound of formula
Figure imgb0009
worin Rf, R1, X, Alk, Q und n die in Anspruch 1 angegebenen Bedeutungen haben, mit einer bifunktionellen Verbindung der Formel
Figure imgb0010
worin R, und R, die in Anspruch 1 angegebenenen Bedeutungen haben, bei einer Temperatur zwischen -20 und 100°C in Gegenwart oder Abwesenheit eines inerten organischen Lösungsmittels und eines Katalysators umsetzt.
Figure imgb0009
 wherein R f , R 1 , X, Alk, Q and n have the meanings given in claim 1, with a bifunctional compound of the formula
Figure imgb0010
 wherein R, and R, which have the meanings given in claim 1, at a temperature between -20 and 100 ° C in the presence or absence of an inert organic solvent and a catalyst.
EP85810436A 1984-10-01 1985-09-25 Diperfluoroalkyl carbamyl acrylates and methacrylates Expired EP0177447B1 (en)

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