EP0177447B1 - Diperfluoroalkyl carbamyl acrylates and methacrylates - Google Patents

Diperfluoroalkyl carbamyl acrylates and methacrylates Download PDF

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EP0177447B1
EP0177447B1 EP85810436A EP85810436A EP0177447B1 EP 0177447 B1 EP0177447 B1 EP 0177447B1 EP 85810436 A EP85810436 A EP 85810436A EP 85810436 A EP85810436 A EP 85810436A EP 0177447 B1 EP0177447 B1 EP 0177447B1
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carbon atoms
formula
alk
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vinyl
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EP0177447A1 (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 wherein R f for perfluoroalkyl, omega-hydroperfluoroalkyl or perfluoroalkoxy-perfluoroalkyl, R j for alkylene with 1 to 12 carbon atoms, X for ⁇ S ⁇ or ⁇ SO 2 -, alk for alkanetriyl 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 2 for alkylene with 1 to 12 carbon atoms and R 3 for hydrogen or methyl.
  • Another object of this invention is a process for the preparation of such acrylate and methacrylate monomers.
  • the Rr 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 Rr group can be straight-chain or branched.
  • Such R r 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 2 preferably denotes alkylene with 2 to 6 carbon atoms, particularly preferably straight-chain alkylene with 2 to 6 carbon atoms and very particularly preferably ethylene.
  • R 3 is particularly preferably methyl.
  • X is preferably ⁇ S ⁇ .
  • Alk is preferably alkanetriyl having 1 to 7 carbon atoms if n is 1.
  • the R f ⁇ R 1 ⁇ X groups are expediently bound to the same carbon atom as the phenylene part.
  • Alk preferably means wherein the R f ⁇ R 1 ⁇ X groups are attached to the ⁇ CH 2 parts.
  • alk is alkanetriyl having 2 to 14, preferably 2 to 6, carbon atoms, the R r -R 1 -X groups are bonded to the same carbon atom and n is zero.
  • the carbamate oxygen is expediently bound to a different carbon atom than those R for ⁇ R i ⁇ X groups.
  • Alk is alkane triyl of 3 to 14 carbon atoms and the R f -R 1 -X groups are attached to adjacent carbon atoms.
  • Q is preferably optionally methyl- or methoxy-substituted phenylene.
  • 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 2 and R 3 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.
  • This process can be conveniently carried out in the presence or absence of a conventional catalyst, such as a urethane catalyst, e.g. B. dibutyltin dilaurate and / or a tertiary amine including trialkylamines, dialkylaralkylamines, dialkylarylamines, N-alkyltheterocyclic amines and aromatic-heterocyclic amines, such as. B. triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, N-methylpiperidine or pyridine. Since the reaction takes place under addition, no significant by-products are formed, which simplifies cleaning and extraction. Often the reaction product can be used without any purification of the desired product. Otherwise, the vinyl monomer can be purified by conventional crystallization methods and obtained by filtering and evaporating.
  • a urethane catalyst e.g. B. dibutyltin dilaurate and / or a
  • the starting materials of the formula (3) are known from the prior art.
  • the monomers of the formula (3) are described, for example, in US Pat. Nos. 2,718,516 and 2,821,544 and in J. Coatings Technology, Volume 55, (703), pp. 55-61 (1983).
  • Monomers of the formula (3) are preferred in which R 2 is alkylene with 2 to 6 carbon atoms and R 3 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 ⁇ , B-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 ⁇ X ⁇ H, where R f and R 1 have the meanings given above and X is S, according to the in Example 2 of U.S. Patent 3,883,596 procedure.
  • 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
  • R r acrylate and R f methacrylate monomers according to the invention are 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 catalyst Come as a suitable catalyst all of the generally known means of 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, non-ionic surfactants in which a poly (ethoxy) group is present as the hydrophilic group and either a hydrocarbon or fluorocarbon group is present as the hydrophobic part, such as.
  • non-ionic surfactants in which a poly (ethoxy) group is present as the hydrophilic group and either a hydrocarbon or fluorocarbon group is present as the hydrophobic part, such as.
  • B. 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.
  • a suitable solvent such as.
  • fluorinated solvents for example hexafluoroxylene, trifluorotoluene or mixtures thereof 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 one Reaction vessel at 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 3 , X, Alk, Q and n have the meanings given above.
  • hydrophilic comonomers are expediently used. If both hydrophobic and oleophobic 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 widely depending on the degree of oleophobization and, if appropriate, 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.
  • vinyl acetate and vinyl esters of substituted acids such as vinyl methoxy acetate.
  • 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.
  • Perfluorinated side chain-containing vinyl monomers can also be used as comonomers with some of the new monomers of the formula (1).
  • Examples of such perfluorinated monomers are vinyl esters containing fluorinated alkyl groups, which are disclosed in U.S. Patents 2,592,069 and 2,436,144.
  • Other useful monomers are acrylates and methacrylates and their derivatives, such as those known from US Patents 2,628,958, 3,256,230, 2,839,513, 3,282,905, 3252932 and 3,304,278.
  • a small amount of other reactive comonomer e.g. B. to improve the properties of the new textile equipment obtained in the use of this invention in washing and dry cleaning.
  • 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 used.
  • Such reactive monomers which can be used are acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylolacrylamide, 2-hydroxyethyl methacrylate or acrylate, hydroxypropyl acrylate or methacrylate and t-butylaminoethyl methacrylate and glycidyl methacrylate.
  • N-methylolacrylamide and 2-hydroxyethyl methacrylate are preferred.
  • Coatings made from the homopolymers and copolymers according to the invention can be prepared as solutions or aqueous emulsions and applied from these.
  • Suitable solvents are, for. B. fluoroalkanes, 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 a, a, a-trifluorotoluene, also known as benzotrifluoride, hexafluoroxylene and their mixtures with ethyl acetate or acetone.
  • concentrations of the fluorinated polymers according to the invention in the solvent for producing coatings with effective 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.
  • non-fluorinated polymers which can be used in such mixtures include, 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 water, methylene iodide and hexadecane.
  • NMR shows proton resonances at 8 1.99, 3 C (CH 3 ) CH 2 protons; ⁇ 2.94.8 (C 8 F 17 CH 2 CH 2 S) 2 protons; ⁇ 3.57.2 NHCH 2 CH 2 O 2 C protons; ⁇ 3.85, 3 COCH 3 protons; 8 4.29.2 NHCH 2 CH 2 O 2 C protons; ⁇ 5.5, 1 S 2 CH ⁇ C proton; ⁇ 5.69, 1 proton and ⁇ 6.19, 1 C (CH 3 ) CH 2 proton; ⁇ 7.00, 1 NH proton; 8 7.13, 2 (CH) 2 protons and ⁇ 7.29, 1 CHC (OCH 3 ) proton.
  • 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 obtained as a white crystalline solid with a melting point of 55-56 ° C.
  • NMR shows proton resonances at 8 1.93, 3 C (CH 3 ) CH 2 protons; ⁇ 2.13-3.33, 10 R f CH 2 CH 2 SCH (CH 2 SCH 2 CH 2 R f ) protons; ⁇ 3.47, 2 O 2 CNHCH 2 CH 2 protons and 1 SCH (CH 2 SCH 2 CH 2 R f ) proton; 8 4,23,4 NHCH 2 CH 2 0 2 C and CHCH 2 O 2 C protons; ⁇ 4.87, 1 NH proton; 8 5.55 and 8 6.11, 2 C (CH 3 ) CH protons.
  • Polymer films are made on glass plates and these show the following contact angles (degrees):

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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 Formel

Figure imgb0001
worin Rf für Perfluoralkyl, omega-Hydroperfluoralkyl oder Perfluoralkoxy-perfluoralkyl, Rj für Alkylen mit 1 bis 12 Kohlenstoffatomen, X für ―S― oder ―SO2―, AlkfürAlkantriyl 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.The present invention thus relates to new diperfluoroalkylcarbamyl acrylates and methacrylates - and polymers thereof - of the formula
Figure imgb0001
 wherein R f for perfluoroalkyl, omega-hydroperfluoroalkyl or perfluoroalkoxy-perfluoroalkyl, R j for alkylene with 1 to 12 carbon atoms, X for ―S― or ―SO 2 -, alk for alkanetriyl 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 2 for alkylene with 1 to 12 carbon atoms and R 3 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 RrGruppe 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 Rr Gruppe kann geradkettig oder verzweigt sein. Solche RrGruppen sind bevorzugt, die Perfluoralkylreste darstellen, wie die perfluorierten Derivaste von Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl und Dodecyl sowie deren Isomere, wobei ein Gemisch aus Perfluoralkylresten Rf besonders vorteilhaft ist.The Rr 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 Rr group can be straight-chain or branched. Such R r 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.

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 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.

R2 bedeutet vorzugsweise Alkylen mit 2 bis 6 Kohlenstoffatomen, besonders bevorzugt geradkettiges Alkylen mit 2 bis 6 Kohlenstoffatomen und ganz besonders bevorzugt Aethylen.R 2 preferably denotes alkylene with 2 to 6 carbon atoms, particularly preferably straight-chain alkylene with 2 to 6 carbon atoms and very particularly preferably ethylene.

R3 ist besonders bevorzugt Methyl.R 3 is particularly preferably methyl.

X steht vorzugsweise für ―S―.X is preferably ―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

Figure imgb0002
worin die Rf―R1―X-Gruppen an die ―CH2-Teile gebunden sind.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 means
Figure imgb0002
 wherein the R f ―R 1 ―X groups are attached to the ―CH 2 parts.

In einer weiteren Ausführungsform bedeutet Alk Alkantriyl mit 2 bis 14, vorzugsweise 2 bis 6 Kohlenstoffatomen, sind die Rr-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―Ri―X-Gruppen.In a further embodiment, alk is alkanetriyl having 2 to 14, preferably 2 to 6, carbon atoms, the R r -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 for ―R i ―X groups.

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.In yet another embodiment, Alk is alkane triyl of 3 to 14 carbon atoms and the R f -R 1 -X groups are attached to adjacent carbon atoms.

Q bedeutet vorzugsweise gegebenenfalls methyl- oder methoxysubstituiertes Phenylen.Q is preferably optionally methyl- or methoxy-substituted phenylene.

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

Figure imgb0003
worin Rf, R1, X, Alk, Q und n die oben angegebenen Bedeutungen haben, mit einer bifunktionellen Verbindung der Formel
Figure imgb0004
worin R2 und R3 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-Alkyltheterocyclischen 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 verlaüft, entstehen keine Nebenprodukte in bedeutsamen Ausmass, wodurch sich die Reinigung und Gewinnung vereinfacht. Häufig lässt sich das Reaktionsprodukt ohne irgendwelche Reinigung des gewünschten Produkts verwenden. Andernfalls 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 imgb0003
 wherein R f , R 1 , X, Alk, Q and n have the meanings given above, with a bifunctional compound of the formula
Figure imgb0004
 wherein R 2 and R 3 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. B. petroleum ether, 1,1,2-trichlorotrifluoroethane, methyl ethyl ketone, toluene, 2-ethoxyethyl acetate, hexafluoroxylene. This process can be conveniently carried out in the presence or absence of a conventional catalyst, such as a urethane catalyst, e.g. B. dibutyltin dilaurate and / or a tertiary amine including trialkylamines, dialkylaralkylamines, dialkylarylamines, N-alkyltheterocyclic amines and aromatic-heterocyclic amines, such as. B. triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, N-methylpiperidine or pyridine. Since the reaction takes place under addition, no significant by-products are formed, which simplifies cleaning and extraction. Often the reaction product can be used without any purification of the desired product. Otherwise, the vinyl monomer can be purified by conventional crystallization methods and obtained by filtering and evaporating.

Die Ausgangsstoffe der Formel (3) sind aus dem Stand der Technick bekannt. Die Monomeren der Formel (3) sind beispielsweise in den U.S. Patenten 2 718 516 und 2 821 544 sowie in J. Coatings Technology, Band 55, (703), S. 55-61 (1983) beschrieben. Solche Monomere der Formel (3) werden bevorzugt, worin R2 für Alkylen mit 2 bis 6 Kohlenstoffatomen und R3 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 the formula (3) are known from the prior art. The monomers of the formula (3) are described, for example, in US Pat. Nos. 2,718,516 and 2,821,544 and in J. Coatings Technology, Volume 55, (703), pp. 55-61 (1983). Monomers of the formula (3) are preferred in which R 2 is alkylene with 2 to 6 carbon atoms and R 3 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,B-ungesättigten Estermonomeren der Formel (1) sind sehr reaktionsfähig und besitzen eine starke Tendenz zur Bildung von Homo- oder Copolymeren.The present α, B-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 4 429 162 beschrieben und solche, worin Alk der Formel

Figure imgb0005
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 of the formula
Figure imgb0005

entspricht, im U.S. Patent 3 883 596 als Beispiel angegeben.corresponds in U.S. Patent 3,883,596 given as an example.

Ferner werden solche Verbindungen der Formel (2), worin Alk für Alkantriyl mit 2 bis 14 Kohlenstoffatomen steht, die Rf―R1―X-Gruppen an dasselbe Kohlenstoffatom gebunden sind und n null ist, unter anderem durch Reduktion der in U.S. Patent 4 239 915 beschriebenen Monocarbonsäure zu den entsprechenden 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 Alkohols 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 f ―R 1 ―X groups are bonded to the same carbon atom and n is zero, inter alia by reducing the number in US Pat 239 915 described monocarboxylic acid 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 entsprechenden halogensubstituierten Alkylepoxids mit zwei Mol Rf―R1―X―H herstellen, worin Rf und R1 die oben angegebenen Bedeutungen haben und X für ­S­ steht, gemäss der in Beispiel 2 des U.S. Patents 3 883 596 angegebenen Arbeitsweise. Als Ausgangsstoff kann man dabei auch die im U.S. Patent 4 158 672 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 ―X ― H, where R f and R 1 have the meanings given above and X is S, according to the in Example 2 of U.S. Patent 3,883,596 procedure. 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 Polymerisation der erfindungsgemässen RrAcrylat- und Rf-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 r acrylate and R f 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 bevorzugt.The 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. Come as a suitable catalyst all of the generally known means of 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 Textilbehandlungsbädern 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, non-ionic surfactants in which a poly (ethoxy) group is present as the hydrophilic group and either a hydrocarbon or fluorocarbon group is present as the hydrophobic part, such as. B. 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 zweickmässigsten 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 Hexafluorxylol, 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. B. fluorinated solvents, for example hexafluoroxylene, trifluorotoluene or mixtures thereof 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 one Reaction vessel at 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 imgb0006
worin Rf, R1' R2, R3, 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 oleophobe Eigenschaften erwünscht, so besitzen die herkömmlichen Comonomeren vorteilhafterweise vorwiegend hydrophoben Charakter, um optimale Ergebnisse zu erzielen. Während die Menge an in der Copolymerisation 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 imgb0006
 wherein R f , R 1 ' R 2 , R 3 , 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 oleophobic 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 widely depending on the degree of oleophobization and, if appropriate, 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 Copolymeren der neuen Monomeren der Formel (1) verwendbare Comonomere sind zum Beispiel: Aethylen, sowie Chlor-, Fluor-, Amido- und Cyanderivate des Aethylens, wie Vinylchlorid, Vinylidenchlorid, Vinylfluorid, Acrylnitril, Methacrylnitril, Acrylamid, Methacrylamid und N,N-Dimethylacrylamid, Tetrafluoräthylen und Hexafluorpropylen ; Acrylat- und Methacrylatmonomere, insbesondere solche mit 1 bis 18 Kohlenstoffatomen 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-Methoxyäthylacrylat und Phenylacrylat ; Diene, insbesondere 1,3-Butadien, Isopren und Chloropren, 2-Fluorbutadien, 1,1,3-Trifluorbutadien, 1,1,2,3-Tetrafluorbutadien, 1,1,2-Trifluor-3,4-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. Vinylacetat und Vinylester substituierter Säuren wie beispielsweise Vinylmethoxyacetat. Vinyltrimethylacetat, Vinylisobutyrat, Isopropenylbutyrat, Vinyllactat, Vinylcaprylat, Vinylpelargonat, Vinylmyristat, Vinyloleat und Vinyllinoleat ; sowie Vinylester aromatischer Säuren wie Vinylbenzoat. Propylen, Butylen und lsobutylen sind die bevorzugten a-Olefine zur Verwendung als Comonomere mit den neuen Fluormonomeren der Formel (1), wobei geradkettige und verzweigte a-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 Vinylmonomere verwendbar. Beispiele für solche perfluorierte Monomere sind fluorierte Alkylgruppen enthaltende Vinylester, die in U.S. Patenten 2 592 069 und 2436144 offenbart sind. Weitere nützliche Monomere sind Acrylate und Methacrylate sowie deren Derivate, wie solche, die aus U.S. Patenten 2628958, 3 256 230, 2839513, 3 282 905, 3252932 und 3 304 278 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, especially 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-methylpylacrylate , Tetradecyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate 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-trifluoro-3,4-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 readily 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, e.g. B. vinyl acetate and vinyl esters of substituted acids such as vinyl methoxy acetate. Vinyl trimethyl acetate, vinyl isobutyrate, isopropenyl butyrate, vinyl lactate, 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. Perfluorinated side chain-containing vinyl monomers can also be used as comonomers with some of the new monomers of the formula (1). Examples of such perfluorinated monomers are vinyl esters containing fluorinated alkyl groups, which are disclosed in U.S. Patents 2,592,069 and 2,436,144. Other useful monomers are acrylates and methacrylates and their derivatives, such as those known from US Patents 2,628,958, 3,256,230, 2,839,513, 3,282,905, 3252932 and 3,304,278.

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 Vernetzungsmittel beim Härtungsvorgang und werden im allgemeinen in Mengen von 0.01 % bis 5 %, vorzugsweise 0,1 % 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. B. to improve the properties of the new textile equipment obtained in the use of this invention in washing and dry cleaning. 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 used.

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

Beschichtungen aus den erfindungsgemässen Homopolymeren und Copolymeren können als Lösungen oder wässrige Emulsionen hergestellt und aus diesen aufgebracht werden. Als Lösungsmittel eignen sich z. B. Fluoralkane, Fluorchloralkane, fluoralkylsubstituierte Aromaten, Alkylester von Perfluoralkansäuren, chlorierte Alkane oder Aromaten, aromatische Kohlenwasserstoffe, Ketone, Ester und Aether. Besonders zweckmässige Lösungsmittel sind fluorierte Lösungsmittel und insbesondere a,a,a-Trifluortoluol, auch als Benzotrifluorid bekannt, Hexafluorxylol 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 erfindungsgemässen Polymeren mit vermischten 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 solchen Gemischen verwendbare nichtfluorierte Polymere sind, ohne darauf beschränkt zu sein, Polymere und Copolymere von Alkylacrylaten und Alkylmethacrylaten, wie Methylmethacrylat, Aethylmethacrylat, Hexylmethacrylat und n-Octylmethacrylat. Poly-n-octylmethacrylat ist als solches Polymer besonders geeignet. Ferner kommen Polymere und Copolymere von Acrylsäure, Methacrylsäure, Styrol, Alkylstyrol, Butadien, 2-Methyl-1,3-butadien, 2-Chlor-1,3-butadien, Polymere und Copolymere von Vinylestern 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 Allylestern wie Allylpropionat oder Allylcaprylat, Polymere und Copolymere von Vinyläthern wie Methylvinyläther, Cetylvinyläther, sowie Polymere und Copolymere von Acrylamid, Methacrylamid, N-Methylolacrylamid, N-Methylolmethacrylamid, N-Isopropylacrylamid und Methacrylnitril dabei in Frage.Coatings made from the homopolymers and copolymers according to the invention can be prepared as solutions or aqueous emulsions and applied from these. Suitable solvents are, for. B. fluoroalkanes, 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 a, a, a-trifluorotoluene, also known as benzotrifluoride, hexafluoroxylene 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 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 include, 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 ethers such as methyl vinyl ether, cetyl vinyl ether, and also of acryl amide copolymers 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 Kontaktwinkeis 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 water, methylene iodide and hexadecane.

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

Beispiel 1example 1 4-[Methenyl-(bis-1,1,2,2-tetrahydroperfluordecyithio)]-2-methoxy-phenoxycarbonylamidoäthyl-methacrylat4- [Methenyl- (bis-1,1,2,2-tetrahydroperfluorodecyithio)] - 2-methoxy-phenoxycarbonylamidoethyl methacrylate

Man bringt 3 g (2,742 mMol) 4-[Methenyl-(bis-1,1,2,2-tetrahydroperfluordecylthio)]-2-methoxyphenol (vgl. U.S. Patent 4429 162) unter Stickstoff in 15 ml Hexan bei 50 °C-55 °C 12 Stunden lang in Gegenwart katalytischer 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 Formel3 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 imgb0007
als weissen kristallinen Feststoff vom Schmelzpunkt 84 °C erhält. NMR zeigt Protonenresonanzen bei 8 1,99, 3 C(CH3)CH2-Protonen ; δ 2,94, 8 (C8F17CH2CH2S)2-Protonen ; δ 3,57, 2 NHCH2CH2O2C-Protonen ; δ 3,85, 3 COCH3-Protonen ; 8 4,29, 2 NHCH2CH2O2C-Protonen ; δ 5,5, 1 S2CH―C-Proton ; δ 5,69, 1 Proton und δ 6,19, 1 C(CH3)CH2-Proton ; δ 7,00, 1 NH-Proton ; 8 7,13, 2 (CH)2-Protonen und δ 7,29, 1 CHC(OCH3)-Proton.
Figure imgb0008
Figure imgb0007
 obtained as a white crystalline solid with a melting point of 84 ° C. NMR shows proton resonances at 8 1.99, 3 C (CH 3 ) CH 2 protons; δ 2.94.8 (C 8 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 3 protons; 8 4.29.2 NHCH 2 CH 2 O 2 C protons; δ 5.5, 1 S 2 CH ― C proton; δ 5.69, 1 proton and δ 6.19, 1 C (CH 3 ) CH 2 proton; δ 7.00, 1 NH proton; 8 7.13, 2 (CH) 2 protons and δ 7.29, 1 CHC (OCH 3 ) proton.
Figure imgb0008

Beispiel 2Example 2 2-[2,3-(Bis-1,1,2,2-tetrahyd ropertluoralkylthio)-propyloxycarbonyl]-aminoäthyl-methacrylat2- [2,3- (bis-1,1,2,2-tetrahydrofluoroalkylthio) propyloxycarbonyl] aminoethyl methacrylate

Man bringt 10,0 g (21,85 mMol) 2,3-[Bis-1,1,2,2-tetrahydroperfluoralkylthio)-1-propanol] (vgl. U.S. Patent 3 883 596) 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-lsocyanatoäthyl-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

Figure imgb0009
als weissen kristallinen Feststoff vom Schmelzpunkt 55-56 °C erhält. NMR zeigt Protonenresonanzen bei 8 1,93, 3 C(CH3)CH2-Protonen ; δ 2,13-3,33, 10 RfCH2CH2SCH(CH2SCH2CH2Rf)-Protonen ; δ 3,47, 2 O2CNHCH2CH2-Protonen und 1 SCH(CH2SCH2CH2Rf)-Proton; 8 4,23, 4 NHCH2CH202C- und CHCH2O2C-Protonen ; δ 4,87, 1 NH-Proton ; 8 5,55 und 8 6,11, 2 C(CH3)CH-Protonen.10.0 g (21.85 mmol) of 2,3- [bis-1,1,2,2-tetrahydroperfluoroalkylthio) -1-propanol] (see US Pat. No. 3,883,596) with an average molecular weight of 457.5 are placed under nitrogen in 270 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
Figure imgb0009
 obtained as a white crystalline solid with a melting point of 55-56 ° C. NMR shows proton resonances at 8 1.93, 3 C (CH 3 ) CH 2 protons; δ 2.13-3.33, 10 R f 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; 8 4,23,4 NHCH 2 CH 2 0 2 C and CHCH 2 O 2 C protons; δ 4.87, 1 NH proton; 8 5.55 and 8 6.11, 2 C (CH 3 ) CH protons.

Beispiel 3Example 3

Polymer des 2-[2,3-Bis-1,1,2,2-tetrahydroperfluoralkylthio)-propyloxycarbonyl]-aminoäthyl-methacrylatsPolymer of 2- [2,3-bis-1,1,2,2-tetrahydroperfluoroalkylthio) propyloxycarbonyl] aminoethyl methacrylate

Man löst 3 g 2-[2,3-Bis-1,1,2,2-tetrahydroperfluoralkylthio)-propyloxycarbonyl]-aminoäthyl-methacrylat und 0,1 g 1,1'-Azobis-(cyancyclohexan) in 27 g Hexafluorxylol, 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 8 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 (cyanocyclohexane) are dissolved in 27 g of hexafluoroxylene, flushes with nitrogen, melts in a vacuum in a vacuum and polymerizes for 12 hours at 95 ° C. in a stirred bath. NMR shows no proton resonances in the range 8 5-6.5.

Beispiel 4Example 4 Polymer des 4-[Methenyl-(bis-1,1,2,2-tetrahydroperfluordecylthio)]-2-methoxy-phenoxycarbonylamino- äthyl-methacrylatsPolymer of 4- [methenyl- (bis-1,1,2,2-tetrahydroperfluorodecylthio)] - 2-methoxy-phenoxycarbonylamino-ethyl methacrylate

Man löst 1,5 g 4-[Methenyl-(bis-1,1,2,2-tetrahydroperfluordecylthio)]-2-methoxy-phenoxycarbonyla- minoäthyl-methacrylat 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 8 5-6,5.1.5 g of 4- [methenyl- (bis-1,1,2,2-tetrahydroperfluorodecylthio)] - 2-methoxy-phenoxycarbonylaminoethyl methacrylate and 0.075 g of 1,1'-azobis (cyanocyclohexane) are dissolved in 13 , 5 g hexafluoroxylene, flushes with nitrogen, melts in a vacuum in a vacuum and polymerizes for 12 hours at 95 ° C. in a stirred bath. NMR shows no proton resonances in the range 8 5-6.5.

Beispiel 5Example 5

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

Figure imgb0010
Polymer films are made on glass plates and these show the following contact angles (degrees):
Figure imgb0010

Claims (16)

1. A compound of the formula
Figure imgb0016
wherein Rf is perfluoroalkyl, omega-hydroperfluoroalkyl, or perfluoroalkoxy substituted perfluoroalkyl, R1 is alkylene having from 1 to 12 carbon atoms, X is ―S― or ―SO2―, Alk is alkanetriyl having from 1 to 14 carbon atoms, Q is phenylene or phenylene which is substituted by chlorine, bromine, alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms, n is 0 or 1, R2 is alkylene having from 1 to 12 carbon atoms and R3 is hydrogen or methyl.
2. A compound according to claim 1, wherein Rt contains from 1 to 18 carbon atoms.
3. A compound according to claim 2, wherein Rf is perfluoroalkyl.
4. A compound according to claim 3, wherein R2 is alkylene of 2 to 6 carbon atoms.
5. A compound according to claim 4, wherein R3 is methyl.
6. A compound according to claim 1, wherein X is ―S―.
7. A compound according to claim 3, wherein Alk is alkanetriyl of 1 to 7 carbon atoms and n is 1.
8. A compound according to claim 3, wherein Alk is
Figure imgb0017
wherein the Rf―Ri―X― groups are attached to the ―CH2― moieties.
9. A compound according to claim 3, wherein Alk is alkanetriyl of 2 to 14 carbon atoms, the Rf―R1―X― groups are attached to the same carbon atom, and n is zero.
10. A compound according to claim 3, wherein Alk is alkanetriyl of 3 to 14 carbon atoms and the Rf―R1―X― groups are attached to adjacent carbon atoms.
11. A compound according to claim 7, wherein X is ―S―.
12. A polymer containing structure units of the formula
Figure imgb0018
wherein Rf, Ri, R2, R3, X, Alk, Q and n are as defined in claim 1.
13. A polymer according to claim 12 which is a homopolymer.
14. A polymer according to claim 12 which is a copolymer.
15. A process for rendering a textile hydrophobic and oleophobic, which comprises coating said textile with a solvent solution or aqueous emulsion of a polymer according to claim 12.
16. A process for the preparation of a compound of the formula (1), which comprises reacting a compound of the formula
Figure imgb0019
wherein Rf, R1, X, Alk, Q and n are as defined in claim 1, with a difunctional compound of the formula
Figure imgb0020
wherein R2 and R3 are as defined in claim 1, at a temperature between -20 and 100 °C in the presence or absence of an inert organic solvent and of a catalyst.
EP85810436A 1984-10-01 1985-09-25 Diperfluoroalkyl carbamyl acrylates and methacrylates Expired EP0177447B1 (en)

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US06/655,833 US4540805A (en) 1984-10-01 1984-10-01 Di-perfluoroalkyl carbamyl group containing acrylates and methacrylates

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US2718516A (en) * 1952-11-08 1955-09-20 Rohm & Haas Isocyanato esters of acrylic, methacrylic, and crotonic acids
US2803656A (en) * 1956-01-23 1957-08-20 Minnesota Mining & Mfg Fluorocarbonsulfonamidoalkanols and sulfates thereof
US3808251A (en) * 1967-05-16 1974-04-30 Du Pont Fluorinated acrylic monomers containing hetero atoms and their polymers
US3445491A (en) * 1967-06-30 1969-05-20 Geigy Chem Corp Perfluoroalkylamido - alkylthio methacrylates and acrylates and intermediates therefor
US3547861A (en) * 1968-04-12 1970-12-15 Allied Chem Novel fluorinated acrylates and polyacrylates
US3654244A (en) * 1970-03-16 1972-04-04 Us Agriculture Polymers for soil-release textile finishes
US3883596A (en) * 1972-08-25 1975-05-13 Pennwalt Corp Fluorine and sulfur-containing compositions
US4125671A (en) * 1977-05-06 1978-11-14 Thiokol Corporation Acrylated dithiocarbamyl esters
US4321404A (en) * 1980-05-20 1982-03-23 Minnesota Mining And Manufacturing Company Compositions for providing abherent coatings
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US4429162A (en) * 1982-02-01 1984-01-31 Ciba-Geigy Corporation Perfluoroalkyl phenols and naphthols

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