HK1128680A - Fluorous telomeric compounds and polymers containing same - Google Patents

Description

FLUORINE-CONTAINING TETRAMERIC COMPOUND AND POLYMER COMPRISING THE SAME

Fluorochemicals are commonly used as surfactants or wetting agents and are widely used in the surface treatment of substrates. Fluorochemicals are commonly used for oil, water and stain repellent finishing (finishing) of fibrous substrates (e.g., carpet, textiles, leather, nonwoven fabrics, and paper) and hard substrates (e.g., wood, metal, or concrete). The substrate thus treated reduces the uptake of hydrophilic and hydrophobic liquids and facilitates the removal of existing soils.

Perfluoroalkyl iodides prepared by telomerization of telogens with fluorinated monomers (e.g., tetrafluoroethylene) are, for example, important starting materials for the preparation of fluorine-containing compounds.

For use as a surface modifying substance, typically the perfluoroalkyl iodide is first converted to perfluoroalkyl ethyl iodide along with ethylene. The perfluoroalkylethyl iodide may then be converted, together with a suitable reagent, into the corresponding perfluoroalkylethyl alcohol. The corresponding (meth) acrylate monomer of formula I can then be prepared from the perfluoroalkylethyl alcohol.

R_FCH₂CH₂OCOCR＝CH₂ (I)

The preparation of fluoroacrylates and methacrylates satisfying formula I from various derivatives of acrylic acid and methacrylic acid, respectively, is well known and documented.

Copolymers prepared from these fluoroacrylates are particularly useful for modifying surfaces to be oil, water and stain repellent, for example for finishing textiles or for coating leather and paper.

The fluoromonomers of formula II are known for similar applications

R_FSO₂NR′(CH₂)_nOCOCR＝CH₂ (II)

Fluorinated alkyl sulfonic acid fluorides (fluorinated alkyl sulfonic acid fluorides) for their synthesis are prepared by electrochemical fluorination.

It has been determined that for both monomer types (I and II), coated surfaces containing longer (and ideally straight chain) perfluoroalkyl chains consisting of 8-10 fluorinated carbon atoms have particularly low surface energies.

Fluorochemical compounds containing a linear perfluoroalkyl chain having 8 fluorinated carbon atoms (including the monomers described above) can degrade to form perfluorononanoic acid and perfluorooctanesulfonic acid, respectively. These degradation products are not believed to degrade further and therefore persist. Furthermore, these compounds are suspected to accumulate in the organism.

Therefore, in recent years, various proposals have been made for the preparation of perfluoroalkyl compounds compatible with the environment.

WO 02/16306 describes branched fluorine-containing (meth) acrylates having the structure of formula III,

R_F(R_F′)CHOCOCR＝CH₂ (III)

the compound contains a linear or branched perfluoroalkyl group R having 5 or less carbon atoms_FAnd a branched perfluoroalkyl chain R having 3 to 5 carbon atoms_F'. These compounds in particular give degradation products of low molecular weight and low toxicity.

Shorter-chain perfluoroalkylsulfonic acid derivatives are known to be more easily eliminated from living organisms. WO03/062521 describes textile finishing agents based on perfluorobutanesulfonic acid derivatives corresponding to formula II instead of perfluorooctanesulfonic acid derivatives containing a partially branched perfluoroalkyl group RF having 4 fluorinated carbon atoms

R_FSO₂NR′(CH₂)_nOCOCR＝CH₂ (II)

Wherein, n is 1, 2, R' is H, alkyl, R is H, CH₃。

Compounds containing fluorinated alkyl groups having 4 carbon atoms and corresponding to formula I

R_FCH₂CH₂OCOCR＝CH₂ (I)

As described in EP-1632542. It is likely that degradation products are more easily eliminated from the organism.

WO 02/34848 describes the use of polyoxetanes having trifluoromethyl or pentafluoroethyl as perfluoroalkyl group. Such compounds also represent environmentally compatible perfluoroalkyl-containing compounds for use as fluorosurfactants or in coatings.

WO 2004/060964 describes fluorinated polyethers having a molecular weight of more than 750g/mol which are particularly easy to eliminate from the organism. WO 03/100158 describes the use of such alcohols and acrylates in the finishing of textiles.

However, it has been shown that environmentally friendly alternatives to perfluoroalkyl compounds proposed to date are less effective than perfluoroalkyl compounds when used as a base for oil and water repellent finishes. This is reflected in the water and oil repellency values and coating durability.

It is an object of the present invention to provide an alternative to polyfluoroalkyl group-containing compounds and derivatives thereof which do not have a bioaccumulation effect. Its properties also include high efficiency when used as an oil and water repellent coating. Furthermore, the compounds must remain operable on an industrial scale.

Surprisingly, it has now been found that polyfluoroalkyl compounds as defined below yield oil and water repellent coatings that are highly efficient and durable and also environmentally compatible.

Accordingly, the present invention provides fluoroalcohol-functional, methacrylate-functional and/or acrylate-functional telomeric compounds having a molecular weight greater than 750 g/mol.

The present invention also provides a fluorine-containing compound which, because it consists of a partially branched and partially linear polyfluoroalkyl chain, melts at a lower temperature than an equimolecular weight compound consisting of a linear polyfluoroalkyl chain.

The present invention also provides fluoroalcohol-functional, methacrylate-functional or acrylate-functional telomeric compounds prepared from the corresponding fluoroalkyl iodides by telomerization in one or more stages.

The invention also provides for the preparation of copolymers of methacrylate-functional or acrylate-functional telomeric compounds.

The invention also provides the use of a particular compound or copolymer thereof in applications to reduce the surface energy of a substrate.

The present invention also provides the use of the copolymers described herein for the preparation of compositions for the oil, water and stain repellency of fibrous substrates (e.g., carpet, textile, leather, nonwoven and paper) and hard substrates (e.g., wood, metal or concrete).

The present invention provides a fluorine-containing telomeric compound of formula IV:

R_F-A-[CH₂]_cCR₂R₃-Z (IV)

wherein R is_FIs a perfluoroalkyl group having 1 to 20 carbon atoms,

a is a radical of the formula

Or

R¹Is CF₃、OR₄Cl, Br or I, in the presence of a catalyst,

R₂and R₃Is H, an alkyl group or an aryl group,

R₄is perfluoromethyl, perfluoropropyl or perfluoropropoxypropyl,

x and Y are H, Cl or F,

z is-OH, -OCOCH ═ CH₂or-OCOCCH₃＝CH₂，

a is 0-10, b is 1-30, c is 1-30.

Preferably, the molecular weight of the fluorochemical of formula IV is greater than 750 g/mol. Particular preference is given to compounds of the formula IV having a molecular weight of more than 1000 g/mol.

The polyfluoroalkyl RF may be a polyfluoroalkyl having a single chain length or a mixture of polyfluoroalkyl groups having different chain lengths, e.g., CF₃、C₂F₅、C₃F₇、C₄F₉、C₆F₁₃、C₈F₁₇、C₁₀F₂₁、C₁₂F₂₅、C₁₄F₂₉And C₁₆F₃₁A group. The polyfluoroalkyl group may be branched or unbranched.

Preferably, the compounds of the present invention have a chain length of 1-20 fluorinated carbon atoms and comprise at least one terminal CF₃Saturated polyfluoroalkyl radicals R_F。

Particular preference is given to perfluorocarbon chains R having from 1 to 3 or from 4 to 16 fluorinated carbon atoms_F。

R₁Is a sterically bulky group having a crystallization-inhibiting effect on polyfluoroalkyl chains. Particularly preferred are perfluoromethyl groups, perfluoroalkyl ether groups or chlorine, bromine or iodine atoms. Most preferred is perfluoromethyl.

R₂And R₃Can each be hydrogen, aryl (phenyl) or an alkyl chain having 1 to 4 carbon atoms. Preferably R₂And R₃Each is hydrogen or methyl.

More preferably R₄Is perfluoromethyl, perfluoropropyl or perfluoropropoxypropyl. Most preferred is perfluoromethyl.

Preferably a is 0 to 10, more preferably 0 to 5.

Preferably b is 1-30, more preferably a + b > 3.

Preferably, c is 1 to 30, more preferably c ═ 1.

X and Y may independently be H, Cl or F. Preferably, X and Y are fluorine atoms. Or X is a fluorine atom and Y is a chlorine atom or X and Y are hydrogen atoms.

The fluorine-containing alcohols of formula IV (Z ═ OH) are typically prepared in a multi-step process from the corresponding polyfluoroalkyl-alkyl iodides.

In the first step of the process, known as the telomerization, a fluorine-containing compound capable of transferring free radical chains (telogen) is reacted with at least one fluorinated monomer (backbone) at 20 to 250 ℃ by a free radical formation mechanism to form a telomer of the formula.

R_F-A-I

Useful telogens include fluoroalkyl compounds having a group to be cleaved by a radical, such as fluoroalkyl iodides, bromides, thiols, thioethers, and alcohols. Perfluoroalkyl iodides having a single chain length or mixtures of perfluoroalkyl iodides having different chain lengths are preferred. The perfluoroalkyl iodides may be branched or unbranched, such as perfluoromethyl iodide, perfluoroethyl iodide, perfluoro-n-propyl iodide, perfluoroisopropyl iodide, perfluoro-n-butyl iodide, perfluoroisobutyl iodide, perfluoro-tert-butyl iodide, and various isomers of perfluorohexyl iodide, perfluorooctyl iodide, perfluorodecyl iodide, and perfluorododecyl iodide, and the like.

Preferred perfluoroalkyl iodides of the invention have a chain length of 1 to 20 carbon atoms and at least one terminal CF₃A group.

Particularly preferred are perfluoromethyl iodide, perfluoroethyl iodide, perfluoropropyl iodide or perfluoroisopropyl iodide or a commercial grade mixture of various perfluoroalkyl iodides having chain lengths of 6 to 16 fluorinated carbon atoms or 8 to 16 fluorinated carbon atoms and an average chain length of about 7.5 fluorinated carbon atoms or about 9 fluorinated carbon atoms.

The addition of a backbone to the telogen results in higher molecular weight build-up. The telomers thus formed consist of perfluoroalkyl chains with terminal iodine groups. The manner in which the backbone is incorporated into the telomer will vary depending on which of the three variants below is selected.

First variant, initially only the fluorinated unsaturated monomer CF₂＝CFR₁Added to the telomer. The product is then subjected to telomerization conditions to add the formula CF₂CXY monomer. The telomers thus prepared have the formula

And the monomers are incorporated in a block fashion.

Second variant, starting with the addition of only the fluorinated unsaturated monomer CF₂CXY. The product is then subjected to telomerization conditions to add the formula CF₂＝CFR₁The monomer (2) of (1). The telomers obtained

The monomers are incorporated in block fashion, but the monomers are added in reverse order.

A third variant, the simultaneous addition of a mixture of two monomers, leads to the random incorporation of the monomer CF₂＝CFR₁And CF₂＝CXY。

Formula CF₂＝CFR₁Examples of compounds of (d) are: chlorotrifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, (perfluoropropoxypropyl) vinyl ether, and branched and unbranched perfluoroolefins having a terminal double bond, examples of which are hexafluoropropylene, 1-perfluorobutene, 1-perfluorohexene or perfluorooctene.

Formula CF₂Examples of CXY compounds are, for example, tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, trifluoroethylene, 1-dichloro-2, 2-difluoroethylene and 1-chloro-2, 2-difluoroethylene.

In the case of iodine-containing compounds, the free radicals that initiate the telomerization reaction can be generated by a source that is capable of forming free radicals. Useful sources for free radical formation include light or heat. The light source typically has a maximum emission wavelength in the infrared to ultraviolet region. The radicals are generally formed by heating at from 100 ℃ to 250 ℃.

Useful sources for the formation of free radicals also include the chemical class of free radical initiators, which also reduce the reaction temperature required to form free radicals to 0 ℃ to 150 ℃, examples being organic or inorganic peroxides, azo compounds, organic and inorganic metal compounds and metals, and combinations thereof. Persulfates, fluorinated and non-fluorinated organic peroxides, azo compounds and metals (e.g., Ru, Cu, Ni, Pd and Pt) are particularly preferred.

The telomerization can be carried out in solution, in suspension or in emulsion, without solvent. Particular preference is given to carrying out the reaction in the absence of solvent or in emulsion. If reacted in an emulsion, the telogen is first converted into an aqueous emulsion with the aid of a surfactant. The emulsion may be stabilized by anionic, cationic, nonionic or amphoteric surfactants and combinations thereof. For example, fluorosurfactants are particularly suitable. The reaction is generally carried out at elevated temperature by adding a backbone and a free radical initiator. Other ingredients may increase the reaction yield, examples being small amounts of sulfite, bisulfite or dithionate in aqueous solution.

In the second step of the process, the polyfluoroalkyl iodide so produced is reacted with an olefin under free radical conditions to produce the corresponding substituted or unsubstituted polyfluoroalkylethyl iodide of the formula.

R_F-A-CH₂CR₂R₃I

These olefins are inserted by the free radical process, which can be carried out analogously to the telomerization reaction described above.

Preferred olefins for the addition reaction may be ethylenically unsaturated compounds, such as ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, styrene and 1, 1-diphenylethylene. Ethylene is particularly preferred.

In the third step of the process, the substituted or unsubstituted polyfluorinated ethyl iodide is converted to the corresponding polyfluoroalkylethyl alcohol of the formula.

R_F-A-CH₂CR₂R₃OH

To this end, polyfluoroalkylethyl iodide is hydrolyzed with suitable co-reactants to form the alcohol, for example with the aid of p-toluenesulfonic acid, nitric acid, sulfuric acid, N-methylpyrrolidone, amides and peroxy acids. In a particularly preferred embodiment of the hydrolysis to form the alcohol, the polyfluoroalkylethyl iodide is reacted with N-methylpyrrolidone and water at a temperature of from 100 ℃ to 200 ℃.

In another aspect of the invention, the polyfluoroalkyl iodide of the first step is used to prepare a corresponding substituted or unsubstituted polyfluoroalkyl alkyl alcohol of the formula.

R_F-A-[CH₂]_cCR₂R₃OH

In fact, in the above manner, the polyfluoroalkyl iodide is added to the gamma-enol (alkenol) under suitable conditions. The iodine-containing polyfluoro alcohols thus prepared may be subsequently converted to saturated polyfluoroalkyl alkyl alcohols by prior art hydrogenation. Examples of the gamma-alkenols used are gamma-propenol, gamma-butenol, gamma-pentenol, gamma-hexenol, gamma-heptenol, gamma-decenol and gamma-undecenol.

Alternatively, the polyfluoroalkylethyl iodide of the second step is used to prepare the corresponding substituted or unsubstituted polyfluoroalkylpropyl alcohol of the formula.

R_F-A-[CH₂]₂CR₂R₃OH

To this end, polyfluoroalkylethyl iodide is converted into the corresponding polyfluoroalkyl olefin by dehydroiodination, and subsequently reacted with an aliphatic alcohol (for example methanol, ethanol, butanol or isopropanol) with the aid of a free-radical initiator to form the corresponding substituted or unsubstituted polyfluoroalkylpropyl alcohol.

The polyfluoroalkyl alkyl alcohols produced in these various ways can be reacted with (meth) acrylic acid esters, (meth) acrylic acid or (meth) acryloyl chloride to form the corresponding fluorine-containing (meth) acrylic acid esters of the formula.

R_F-A-[CH₂]_cCR₂R₃OCOCH＝CH₂Or

R_F-A-[CH₂]_cCR₂R₃OCOCCH₃＝CH₂

The reaction with (meth) acryloyl chloride is generally carried out in the presence of a base, such as triethylamine, to bind the hydrogen chloride formed. Suitable catalysts (e.g., tin catalysts) may be used for the transesterification.

These (meth) acrylates may be copolymerized with non-fluorine-containing polymerizable vinyl monomers, thermally crosslinkable or isocyanate-reactive monomers and chlorine-containing polymerizable vinyl monomers.

The present invention also provides a copolymer comprising, based on the total weight of the copolymer:

a) from 20% to 97% by weight and preferably from 40% to 90% by weight of a compound of the formulaIV wherein Z is-OCOCH ═ CH or-OCOCCH₃＝CH，

b) From 0% to 80% by weight and preferably from 10% to 50% by weight of one or more non-fluorine-containing polymerizable vinyl monomers, and/or

c) From 0.5% to 20% by weight and preferably from 1% to 10% by weight of one or more thermally crosslinkable or isocyanate-reactive monomers.

The present invention also provides a copolymer comprising, based on the total weight of the copolymer:

a) from 40% to 90% by weight and preferably from 45% to 85% by weight of monomers of formula IV wherein Z is-OCOCH ═ CH or-OCOCCH₃＝CH，

b) From 0% to 50% by weight and preferably from 0.01% to 30% by weight of one or more non-fluorine-containing polymerizable vinyl monomers, and/or

c) From 0.5% to 20% by weight and preferably from 1% to 10% by weight of one or more thermally crosslinkable or isocyanate-reactive monomers, and

d) from 0.5% to 50% by weight and preferably from 2% to 30% by weight of chlorine-containing polymerizable vinyl monomers.

The optional comonomer (b) is fluorine-free (contains no fluorine) and can be represented by a variety of commercially available acrylate and methacrylate esters and styrene derivatives.

Examples of non-fluorinated comonomers are alkyl esters and amides of unsaturated carboxylic acids. These include, for example, the esters and amides of acrylic acid, methacrylic acid, α -chloroacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid with the following groups: vinyl, allyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 3-dimethylbutyl, heptyl, octyl, isooctyl, dodecyl, hexadecyl, octadecyl, docosyl, cyclohexyl, bornyl, isobornyl, phenyl, benzyl, adamantyl, tolyl, (2, 2-dimethyl-1-methyl) propyl, cyclopentyl, 2-ethylhexyl, 4-ethylcyclohexyl, 2-ethoxyethyl and tetrahydropyranyl.

Other non-fluorinated comonomers are allyl esters and vinyl esters, such as allyl acetate, vinyl acetate, allyl heptanoate and vinyl heptanoate; alkyl vinyl ethers and alkyl allyl ethers such as cetyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether and ethyl vinyl ether; α, β -unsaturated nitriles such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, α -cyanoethyl acrylate; aminoalkyl (meth) acrylates, such as N, N-diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate; alkyl (meth) acrylates having ammonium groups, such as 2-methacryloyloxyethyltrimethylammonium chloride; styrene and its derivatives, such as vinyl toluene, alpha-methyl styrene, alpha-cyanomethyl styrene, chloromethyl styrene; olefins such as ethylene, propylene, isobutylene, butadiene, isoprene; and (meth) acrylates of methoxypolyethylene glycols.

As mentioned above, particularly preferred optional comonomers (b) can be esters or amides of acrylic and methacrylic acid with the following groups: methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, tetradecyl, dodecyl, octadecyl, methoxypoly (ethylene glycol) and methoxypoly (propylene glycol).

Comonomer (c) comprises one or more crosslinkable groups. The crosslinkable group is a functional group capable of reacting with the substrate and/or other polyfunctional compounds added. Such crosslinkable groups may be: a carboxylic acid group, an ethylenically unsaturated group, a hydroxyl group, an amino group, an N-alkanolamide group, an isocyanate group, or a protected isocyanate group. Examples of comonomers having one or more crosslinkable groups include unsaturated carboxylic acids and anhydrides such as acrylic acid, methacrylic acid, alpha-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, poly (ethylene glycol) mono (meth) acrylate, poly (propylene glycol) mono (meth) acrylate, poly (ethylene glycol) mono (meth) acrylate-poly (propylene glycol) mono (meth) acrylate copolymer, polytetrahydrofuran mono (meth) acrylate, N-methylol (meth) acrylamide, hydroxybutyl vinyl ether. Other crosslinkable monomers are, for example, vinyl (meth) acrylate, allyl (meth) acrylate, N-methoxymethylacrylamide, N-isopropoxymethacrylamide, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, glycidyl (meth) acrylate and α, α -dimethyl-m-isopropenylbenzyl isocyanate. Further examples are monomers which release isocyanates at elevated temperature or under light irradiation, examples being phenol-protected, ketoxime-protected and pyrazole-protected isocyanate-terminated alkyl (meth) acrylates.

Optional comonomer (d) is a chlorine-containing comonomer. Examples of chlorine-containing comonomers are halogenated olefins, such as vinyl chloride, vinylidene chloride, 3-chloro-1-isobutene, 1-chloroprene, 1-dichlorobutadiene and 2, 5-dimethyl-1, 5-hexadiene. Vinylidene chloride and vinyl chloride are particularly preferred optional comonomers (c).

The copolymers are typically prepared by free radical polymerization techniques, such as by solvent, emulsion, microemulsion, or mini-emulsion polymerization techniques. A wide variety of emulsion polymerizations are particularly preferred. The emulsion polymerization of the monomers is carried out in the presence of water, a surfactant and optionally an organic solvent. The mixture may be pre-emulsified by a high pressure homogenizer or similar device prior to polymerization. The polymerization is generally carried out in the presence of a free-radical initiator at from 50 ℃ to 150 ℃.

Various anionic, cationic, nonionic or amphoteric surfactants may be used alone or in combination. Examples of nonionic surfactants include poly (ethylene glycol) dodecyl ether, poly (ethylene glycol) tridecyl ether, poly (ethylene glycol) hexadecyl ether, poly (ethylene glycol) -poly (propylene glycol) copolymer hexadecyl ether, poly (ethylene glycol) octadecyl ether, poly (ethylene glycol) oleyl ether, poly (ethylene glycol) nonylphenol ether, poly (ethylene glycol) octylphenol ether, poly (ethylene glycol) monolaurate, poly (ethylene glycol) monostearate, poly (ethylene glycol) monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, poly (ethylene glycol) sorbitan monolaurate, poly (ethylene glycol) sorbitan monopalmitate, Poly (ethylene glycol) sorbitan monostearate, poly (ethylene glycol) sorbitan monooleate, poly (ethylene glycol) -poly (propylene glycol) copolymer, polyglycerol fatty acid ester, polyether-modified silicone oil and perfluoroalkyl-ethylene oxide adduct. The nonionic surfactant is used in an amount of 0.1 to 100% by weight of the polymer.

Examples of cationic surfactants of the invention are ammonium compounds based on saturated and unsaturated fatty acid amines, such as octadecyl ammonium acetate, dodecyl trimethyl ammonium chloride; ammonium compounds based on amino-functional polyethoxylates and polypropoxylates and interpolymers thereof, such as polyoxyethylene dodecylmonomethylammonium chloride; arylamine-based ammonium compounds, such as biphenyltrimethylammonium chloride, imidazoline derivatives such as ammonium salts formed from tallow and imidazoline; silicone-based cationic surfactants and fluorine-based cationic surfactants. The amount of cationic surfactant is 0.1-100% by weight of the polymer.

Examples of the anionic surfactant of the present invention include fatty alcohol sulfates such as sodium lauryl sulfate and poly (ethylene glycol) lauryl ether sulfate; alkyl sulfonates such as sodium dodecyl sulfonate; alkyl benzene sulfonates such as nonylphenol ether sulfate; sulfosuccinates, such as sodium hexadieth sulfosuccinate; fatty alcohol phosphates such as sodium lauryl phosphate; and fatty acid salts, such as sodium stearate. The anionic surfactant is used in an amount of 0.1 to 100% by weight of the polymer.

Examples of free radical initiators are organic or inorganic peroxides, azo compounds, organic and inorganic metal compounds and metals and combinations thereof. Particularly preferred are azo compounds such as Azobisisobutyronitrile (AIBN), azobisvaleronitrile, azobis (2-cyanovaleric acid) and 2, 2' -azobis (2-amidinopropane) dihydrochloride; hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide and tert-amyl hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide; peroxyesters such as t-butyl perbenzoate and di-t-butyl peroxyphthalate; diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; inorganic peroxides such as ammonium persulfate and potassium persulfate and combinations of specific compounds with organic or inorganic metal compounds and metals.

Chain transfer agents may be used for the polymerization, an example of which is alkyl mercaptans.

Examples of organic solvents in solvent and emulsion polymerization are: ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohols such as ethanol, isopropanol, and butanol; polyhydric alcohols such as 1, 3-butanediol, 1, 6-hexanediol, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and glycerol; ethers and esters of polyhydric alcohols such as dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, triethylene glycol dimethyl ether, and diethylene glycol monobutyl ether acetate; esters such as ethyl acetate, propyl acetate, butyl acetate, dibutyl adipate, and dibutyl succinate; hydrocarbons and halogenated hydrocarbons, such as toluene, xylene, octane, perchloroethylene and 1, 3-dichloro-2, 2, 3, 3, 3-pentafluoropropane.

The polymer dispersions prepared preferably have a solids content of from 20 to 40% by weight.

The fluorine-containing copolymers comprising the fluorine-containing monomers of formula IV are suitable for coating fibrous substrates (e.g. carpet, textile, leather, non-woven fabric or paper) or hard substrates (e.g. wood, metal or concrete). The polyfluoro copolymers impart oil, water, and stain repellency to these substrates.

Accordingly, the present invention also provides a method of surface treating a fibrous substrate with an effective amount of the aqueous fluorine-containing dispersion.

The inclusion of the formulation for finishing textiles and other sheetlike structures according to the present invention is selected so that sufficient repellency is imparted to the treated substrate. Wet pick-up was determined by weighing the finished samples before and after application.

The fluorochemical textile-finishing agents of the present invention can be used with other additives including water repellent materials (e.g., waxes, silicones, zirconium compounds, or stearates) as well as other oil repellent materials, surfactants, biocides, flame retardants, antistatic additives, plasticizers, color fixatives, and anti-wrinkle additives in amounts that do not impair the fixation on the textile and the stability of the composition.

The fluorochemical textile-finishing agents of the present invention can be crosslinked by the addition of reactive additives such as melamine resins, blocked isocyanates, or epoxides.

The fibrous substrate to be coated with the fluoropolymer dispersion may be, for example, carpet, textile, leather, nonwoven fabric and paper. These substrates consist in particular of: natural fibers such as cotton, flax, and silk; synthetic fibers such as polyamides, polyesters, polyurethanes, polyolefins, poly (meth) acrylates, poly (vinyl chloride), poly (vinyl alcohol); semi-synthetic fibers such as rayon or acetate; inorganic fibers, for example glass fibers or ceramic fibers or any desired combination of specific fibers or of woven products composed of these materials.

For coating, the substrate is usually immersed in a dilute dispersion consisting of the copolymer and optional additives. Alternatively, the dilute dispersion may be sprayed onto the substrate. The saturated substrate is then pressed by a roller system to remove excess dispersion, dried in an oven, and crosslinked at a temperature and for a time sufficient to ensure crosslinking on the treated substrate. The crosslinking process is typically carried out at 50 to about 190 ℃. Crosslinking is suitable in general at from about 120 ℃ to 180 ℃ and in particular from about 130 ℃ to 170 ℃ for from 20 seconds to 10 minutes, preferably from 5 seconds to 5 minutes.

A further alternative to applying the formulation to a substrate is foam coating, wherein the formulation is applied to the substrate in the form of a foam, followed by drying and crosslinking. For foam coating, the formulation is usually added in concentrated form already mixed with additional blowing agent. Highly concentrated formulations for foam coating typically contain up to 20% by weight of fluoropolymer.

For finishing on textiles, these formulations can be tested in specific tests for water repellency, isopropanol repellency, and oil repellency before and after washing.

Water repellency was tested by spray testing according to AATCC standard test method 22. Distilled water was sprayed onto the textile substrate to be tested and subsequently visually compared to a value in accordance with the evaluation standard description mentioned in the test method. The values reported relate to the appearance of the surface after spraying water and have the following meanings (table 1):

TABLE 1

Water repellency rating	Means of
		100	Without adhering water drops or wetting the upper surface
90	Occasionally adhering water droplets or wetting the upper surface
		80	Wetting the upper surface at the water impact
70	Partially wetting the entire upper surface
		50	Completely wetting the entire upper surface
0	Completely wetting the entire upper and lower surfaces

A second test using a series of water-isopropyl alcohol test solutions can be used to determine the isopropyl alcohol (IPA) repellency of the substrate. The IPA rating recorded is the maximum number of test solutions when the fabric is not wetted within 10 seconds and the drops still have a spherical or hemispherical shape. A wetted substrate or substrate that repels only 100% water (0% isopropyl alcohol), i.e., the lowest wetting test solution, is rated 0, while a substrate that repels 100% isopropyl alcohol (0% water) is rated 10. Intermediate levels may be assigned in the same way.

The oil repellency was tested according to AATCC standard test method 118, testing the ability of the substrate to repel oil, with higher ratings indicating better repellency to such soils (particularly oily liquids). In the test, the wettability is evaluated visually after a specified contact time by applying drops of standardized test liquids consisting of a selected series of hydrocarbons with different surface tensions successively to the surface of the test specimen to be tested by careful suction. The oil repellency value corresponds to the largest numbered test liquid that does not cause surface wetting. The standard test liquid had the following composition (table 2):

TABLE 2

Note: nujol is a mineral oil (available from Plough Inc.) having a Saybolt viscosity of 360/390 at 38 ℃ and a specific gravity of 0.880/0.900 at 15 ℃.

The FC polymers of the prior art have a prevalent oil repellency value of 6; however, class 5 is generally considered to be excellent.

Examples

The following examples illustrate the subject matter and advantages of this invention, but the materials and amounts recited in the examples should not be construed as limiting.

Synthesis of

Example 1:

C₈F₁₇(CF₂CF(CF₃))_a(CF₂CF₂)_bsynthesis of I

An emulsion was prepared by vigorously stirring 110g (0.18mol) Fluowet I812 (claiant), 15g Fluorolink C (Solvay Solexis), 5g of ammonia and 90g of water at 60 ℃ and introduced into the autoclave as a starting material together with 2.5g ammonium persulphate. The pressure was tested after repeated purging with nitrogen. During heating to 80 ℃, hexafluoropropylene and tetrafluoroethylene were added to the stirred emulsion in a ratio of 3: 5 until the total pressure was 17 bar. The pressure was kept constant at 17 bar until 82.5g (0.55mol) of hexafluoropropene and 90g (0.90mol) of tetrafluoroethylene were added. After the pressure had dropped, the autoclave was cooled to room temperature and the fluorochemical phase was separated by adding a salt and washed. The low molecular weight components are separated by distillation. An iodine content of 11.2% indicates an average molecular weight of about 1400 g/mol.

¹⁹F NMR (solvent CDCl)₃/C₆F₆，versus CFCl₃)：-59.8(2F，-CF ₂I) From-71.8 to-77.0 (in each case 3F, -CF-C)F ₃)，-81.9(3F，-CF₂-CF ₃) From-110.2 to-126.9 (in each case 2F, -C)F ₂-, -184.6 to-185.5 (in each case 1F, -C)F(CF₃)-)。

By¹⁹F NMR spectroscopy clearly shows the addition of about 2 molecules of hexafluoropropylene/perfluoroalkyl iodide used.

^*The compound designated fluoet I812 is a mixture of perfluoroalkyl iodides having 6 to 14 fluorinated carbon atoms per molecule and an average chain length of about 9 fluorinated carbon atoms.

Fluorolink C is a perfluoropolyether carboxylic acid.

Examples 2 to 10:

synthesis of polyfluoroalkyl iodides

Example 1 was repeated to prepare the corresponding polyfluoroalkyl iodides (examples 2 to 10). The results of the synthesis are shown in Table 3.

TABLE 3

Conducting a telomerization reaction to produce a polyfluoroalkyl iodide having the following general composition:

example number iodide	RF	RF[mol]	a[mol]	b[mol]	c[mol]	d[mol]	Mn*[kg/mol]
								2	(CF3)2CF-	0.25	0.55	2.23	-	-	1.3
3	C8F17-	0.25	0.71	-	3.06	-	1.5
								4	C2F5-	0.20	0.43	4.04	-	-	2.4
5	C8F17-	0.35	0.68	-	-	1.75	1.2
								6	I812-**	0.30	-	2.49	-	1.23	1.7
7	C8F17-	0.25	-	-	1.98	1.01	1.3
								8	(CF3)2CF-	0.18	0.20	-	1.83	-	0.9
9	I612-**	0.22	0.87	1.32	-	-	1.5
								10	C8F17-	0.26	-	-	-	2.07	1.8

^*Determination from iodine content

^**The compounds designated as fluoet I612 and fluoet I812 are perfluoroalkyl iodide mixtures (available from Clariant) having 6 to 14 fluorinated carbon atoms per molecule and average chain lengths of about 7.5 and 9 fluorinated carbon atoms, respectively.

Example 11:

C₈F₁₇(CF₂CF(CF₃))_a(CF₂CF₂)_bCH₂CH₂synthesis of I

5g H101B/W of a ruthenium-containing catalyst (Degussa) and 173g of the polyfluoroalkyl iodide of example 1 were introduced as starting materials under a nitrogen atmosphere. After pressure testing with 50 bar nitrogen, the autoclave was evacuated to 1 mbar and subsequently cooled to-78 ℃. 10g of ethylene were subsequently condensed at-78 ℃. The reaction mixture was shaken at 170 ℃ for 30 hours. Reduced pressure and filtered to leave 160g of crude product.

¹H NMR (solvent CDCl)₃/C₆F₆)：2.7(2H，-CH₂CH₂I)，3.2(2H，-CH₂CH₂I)。

Examples 12 to 20:

synthesis of polyfluoroalkyl alkyl iodides

Example 11 is repeated to prepare the corresponding polyfluoroalkylalkyliodides (examples 12 to 20). The results of the synthesis are shown in Table 4.

TABLE 4

An olefin is added to produce a polyfluoroalkylalkyl iodide having the following general composition (in each case, c ═ 1):

R_F-A-[CH₂]_cCR₂R₃I

example number Ethyl iodide	Example number iodide	Olefins	Iodide [ mol ]]	Olefin [ mol ]]	Initiator [ g ]]	R2	R3
								12	2	Ethylene	0.08	0.20	5.0	-H	-H
13	3	Propylene (PA)	0.10	0.20	5.0	-H	-CH3
								14	4	Ethylene	0.08	0.20	5.0	-H	-H
15	5	1-butene	0.10	0.30	5.0	-H	-CH2CH3
								16	6	Ethylene	0.05	0.10	2.5	-H	-H
17	7	Isobutene	0.05	0.40	2.5	-CH3	-CH3
								18	8	Ethylene	0.10	0.30	5.0	-H	-H
19	9	Ethylene	0.05	0.10	2.5	-H	-H
								20	10	Ethylene	0.05	0.10	2.5	-H	-H

Example 21:

C₈F₁₇(CF₂CF(CF₃))_a(CF₂CF₂)_bCH₂CH₂synthesis of OH (method A)

Under a nitrogen atmosphere, 65g (0.07mol) of the polyfluoroalkylethyl iodide of example 11 as starting material were introduced together with 83g N-methylpyrrolidone and 25g of deionized water. After pressure testing with 50 bar of nitrogen, the autoclave was shaken at 160 ℃ for 24 hours. After depressurization, the crude product is mixed with 0.5 l of water. And repeatedly washing the fluorine-containing phase by using a sodium chloride solution, and drying to obtain the polyfluoroalkyl ethanol.

¹H NMR (solvent CDCl)₃/C₆F₆)：2.4(2H，-CH ₂CH₂OH)，3.9(2H，-CH₂CH ₂OH)。

Example 22:

C₈F₁₇(CF₂CF(CF₃))_a(CF₂CF₂)_bCH₂CH₂CH₂synthesis of OH (method B)

To prepare the polyfluoroalkylethylene, 310g (0.34mol) of the polyfluoroalkylethyl iodide of example 11 are added dropwise stepwise to a cooled solution of 17.4g of potassium hydroxide in 250ml of ethanol at 0 ℃. The reaction mixture was stirred at room temperature for 1 hour. Filtering the formed potassium iodide, repeatedly washing the polyfluoroalkyl ethylene with water, and drying.

For the reaction to form the alcohol, 800.0g (25.0mol) of methanol were introduced as initial charge into an autoclave equipped with a stirrer, purged with nitrogen and heated to 160 ℃. Next, 290.0g of polyfluoroalkylethylene and 4.8g of di-t-butyl peroxide were placed in a feeding vessel, and fed continuously from the feeding vessel into hot methanol by a metering pump. The feed rate was set so that the polyfluoroalkylethylene-peroxide mixture was added over a period of 3 hours. The pressure in the autoclave was 21 bar. After the metering in, the mixture is held at the stated temperature for a further 2 hours to continue the reaction. To recover the polyfluoroalkylpropanol product formed from the reaction mixture, the excess ethanol is distilled off and the bottom product constituting the polyfluoroalkyl alcohol is washed repeatedly with water.

¹H NMR (solvent CDCl)₃/C₆F₆)：1.9(2H，-CF₂CH₂CH ₂-)，2.1(2H，-CF₂CH ₂CH₂-)，3.7(2H，-CH₂CH ₂OH)。

Example 23:

C₈F₁₇(CF₂CF(CF₃))_a(CF₂CF₂)_b(CH₂)₁₁synthesis of OH (method C)

A solution of 65.0g (0.05mol) of the polyfluoroalkyl iodide of example 1 and 10.0g of 10-undecen-1-ol was heated to 80 ℃ in a three-necked flask equipped with a reflux condenser under a nitrogen atmosphere. Next, 0.15g of initiator 2, 2' -Azobisisobutyronitrile (AIBN) was added. The reaction was maintained at this temperature for 1 hour, at which time the same amount of AIBN was added. The reaction mixture was stirred at 80 ℃ for a further 7 hours. The yield thereof was found to be 85%. After work-up by distillation, 20.0g of the iodine-containing alcohol prepared were cooled to 0 ℃ and purged with nitrogen in a three-necked flask. Then, 12.0g of tributylstannane dissolved in 70ml of tetrahydrofuran was slowly added dropwise. After the addition was complete, the mixture was allowed to warm to room temperature and stirred for an additional 3 hours. The product was obtained by washing (yield 65%).

¹H NMR (solvent CDCl)₃/C₆F₆): 1.2 to 1.8(18H, -CF)₂CH₂(CH ₂)₉-)，2.2(2H，-CF₂CH ₂CH₂-)，3.8(2H，-CH₂CH ₂OH)。

Examples 24 to 30:

synthesis of polyfluoroalkyl alkyl alcohols

Examples 21, 22 and 23 (method A, B, C) were repeated to prepare the corresponding polyfluoroalkyl alcohols (examples 24 to 30). The results of the synthesis are shown in Table 5.

TABLE 5

Carrying out a reaction to produce a polyfluoroalkyl alkyl alcohol having the following general composition:

R_F-A-[CH₂]_cCR₂R₃OH

example No. alkyl alcohols	Examples numbered alkyl iodides or iodides	Method	Alkyl iodides or iodides [ mol ]]	c	R2	R3
							24	12	A	0.05	1	-H	-H
25	13	A	0.05	1	-H	-CH3
							26	14	B	0.05	2	-H	-H
27	15	B*	0.05	2	-H	-CH3
							28	16	A	0.05	1	-H	-H
29	19	A	0.05	1	-H	-H
							30	10	C**	0.05	3	-H	-H

^*Reaction with ethanol

^**Reaction with 1-butenol

Example 31:

C₈F₁₇(CF₂CF(CF₃))_a(CF₂CF₂)_bCH₂CH₂OCOCH＝CH₂(method D)

A three-necked flask was charged with 93g (0.06mol) of the alcohol of example 21, 25.0g of acrylic acid, 0.3g of methanesulfonic acid and 0.4g of p-methoxyphenol and the initial charge was heated to 80 ℃. The water of reaction formed was separated from the reaction at the reaction temperature and the pressure of 200 mbar within 24 hours. The organic phase was washed repeatedly with warm water and dried in a rotary evaporator.

¹H NMR (solvent CDCl)₃/C₆F₆)：2.1(2H，-CH ₂CH₂OH)，4.4(2H，-CH₂CH ₂O-), 5.8 to 6.5(3H, -C)H＝CH ₂)。

Example 32:

C₈F₁₇(CF₂CF(CF₃))_a(CF₂CF₂)_bCH₂CH₂OCOC(CH₃)＝CH₂(method E)

Into a three-necked flask were charged 80g (0.06mol) of the alcohol of example 21, 25g of methacrylic acid, 0.3g of methanesulfonic acid and 0.4g of p-methoxyphenol, and the starting material was heated to 80 ℃. The water of reaction formed was separated from the reaction at the reaction temperature and the pressure of 200 mbar within 24 hours. The organic phase was washed repeatedly with warm water and dried in a rotary evaporator.

¹H NMR (solvent CDCl)₃/C₆F₆)：1.9(3H，-CH ₃)，2.5(2H，-CH ₂CH₂O-)，4.4(2H，-CH₂CH ₂O-), 5.6 to 6.2(2H, -C (CH)₃＝CH ₂)。

Examples 33 to 40:

synthesis of polyfluoroalkyl acrylates

Examples 31 and 32 were repeated to convert the polyfluoroalkyl alcohol to a polyfluoroalkyl (meth) acrylate (examples 33 to 40). The compositions are shown in Table 6.

TABLE 6

The reaction produces a polyfluoroalkyl (meth) acrylate having the following general composition:

R_F-A-[CH₂]_cCR₂R₃OCOCH＝CH₂(method D)

Or

R_F-A-[CH₂]_cCR₂R₃OCOCCH₃＝CH₂(method E)

Example No. (meth) acrylates	EXAMPLES numbered alcohols	c	R2	R3	Method
						33	22	2	-H	-H	D
34	23	10	-H	-H	D
						35	24	1	-H	-H	D
36	25	1	-H	-CH3	D
						37	26	2	-H	-H	D
38	28	1	-H	-H	D
						39	29	1	-H	-H	E
40	30	3	-H	-H	E

Example 41:

dispersion preparation for textile finishing (formulation 1)

In a four-necked flask equipped with a stirrer, reflux condenser, inert gas supply and internal thermometer, a dispersion was prepared by thoroughly stirring the following ingredients:

37.5g of polyfluoroalkyl acrylate (from example 31)

31.0g octadecyl acrylate (SAC)

5.0g Glycidyl Methacrylate (GMA)

4.5g hydroxyethyl methacrylate (HEMA)

30.0g dipropylene glycol

0.4g dodecanethiol

6.0g of dodecanol/16-ethylene oxide adduct (nonionic surfactant A)

4.5g N, N-Dimethyldodecylammonium acetate (cationic surfactant A)

200.0g of water

The emulsion was heated to 60 ℃ under a constant nitrogen flow. Next, 0.2g of initiator 2, 2' -Azobisisobutyronitrile (AIBN) was added. The polymerization time at 60 ℃ was 10 hours.

The resulting dispersion had a solids content of about 34%. For finishing the textiles, the dispersion was acidified and diluted to 30 g/l. The dispersion was applied to a fibrous substrate on a HVF 59301 laboratory padding-mangle (from Mathis AG (switzerland)), followed by drying and heat treatment in an LTE laboratory dryer (from Mathis AG (switzerland)) at 160 ℃ for 30 seconds. A commercially available textile, Sahara 530306 (from NEL GmbH, Neugerdorf) was used as PES/Co 65/35 substrate for comparison of the applications. For all the examples mentioned, the wet pick-up was about 66%. The washing/drying process included 5 washing cycles at 60 ℃. The laundry load was supplemented to 1 kg with the corresponding fabric piece loaded with fabric. The amount of laundry detergent required was 7g "Coral intense"/wash cycle. The fabric pieces did not dry between each wash cycle. After washing, it is dried in a washer dryer.

Example 42:

dispersion preparation for textile finishing (formulation 2)

In an autoclave equipped with a stirrer, reflux condenser and internal thermometer, the following ingredients were thoroughly stirred under an inert atmosphere to prepare a dispersion:

69.5g of polyfluoroalkyl acrylate (from example 31)

19.0g dodecyl acrylate (LA)

8.5g Vinyl Chloride (VC)

2.5g N-Methoxymethylacrylamide (N-MAM)

3.5g hydroxyethyl methacrylate

30.0g dipropylene glycol

0.5g dodecanethiol

7.0g of stearyl alcohol/11 ethylene oxide adduct (nonionic surfactant B)

4.0g dodecyl trimethyl ammonium chloride (cationic surfactant B)

200.0g of water

After heating the emulsion to 60 ℃, 0.6g of initiator 2, 2' -azo-bis-2-amidinopropane dihydrochloride is added. The polymerization time at 60 ℃ was 6 hours. After the reaction, the excess vinyl chloride was removed by stripping.

The resulting dispersion had a solids content of about 38%. For finishing the textiles, the dispersion was acidified and diluted to 30 g/l. Applied to a textile substrate as described in example 41.

Example 43:

dispersion preparation for textile finishing (formulation 3)

In an autoclave equipped with a stirrer, reflux condenser and internal thermometer, the following ingredients were thoroughly stirred under an inert atmosphere to prepare a dispersion:

60.5g of polyfluoroalkyl acrylate (from example 31)

12.5g 2-ethylhexyl acrylate (2-EHAC)

15.0g vinylidene chloride (VDC)

3.5g N-Methoxymethylacrylamide

1.0g of hydroxyethyl methacrylate

35.0g dipropylene glycol

0.7g of dodecanethiol

6.0g of stearyl alcohol/11 ethylene oxide adduct (nonionic surfactant B)

5.0g Sodium Dodecyl Sulfate (SDS)

200.0g of water

After heating the emulsion to 60 ℃, 0.5g of initiator 2, 2' -azo-bis-2-amidinopropane dihydrochloride is added. The polymerization time at 60 ℃ was 6 hours. After the reaction, the excess vinylidene chloride was removed by stripping.

The resulting dispersion had a solids content of about 36%. The dispersion was acidified and mixed with cassurit hml (Clariant) and a 20% by weight aqueous solution of magnesium chloride so that the content was in each case 30g per liter of solution. Applied to a textile substrate as described in example 41.

The results of isopropyl alcohol repellency (IPA), oil repellency (oleo), and water repellency (hydro) are reported in table 7.

Examples 44 to 47:

similar to example 41, a dispersion for textile finishing was prepared, applied and tested.

The dispersion formulations and the results for isopropyl alcohol repellency (IPA), oil repellency (oleo) and water repellency (hydro) are reported in table 7.

Examples 48 to 51:

similar to example 42, a dispersion for textile finishing was prepared, applied and tested.

The dispersion formulations and the results for isopropyl alcohol repellency (IPA), oil repellency (oleo) and water repellency (hydro) are reported in table 7.

Examples 52 to 55:

dispersions for textile finishing were prepared, applied and tested analogously to example 43.

The dispersion formulations and the isopropyl alcohol (IPA), oil (oleo) and water (hydro) repellency results are reported in table 7.

Claims (15)

1. A fluorotelomeric compound of formula IV:

R_F-A-[CH₂]_cCR₂R₃-Z (IV)

wherein R is_FIs a perfluoroalkyl group having 1 to 20 carbon atoms,

a is a radical of the formula

R¹Is CF₃、OR₄Cl, Br or I, in the presence of a catalyst,

R₂and R₃Is H, an alkyl group or an aryl group,

R₄is perfluoromethyl, perfluoropropyl or perfluoropropoxypropyl,

x and Y are H, Cl or,

z is-OH, -OCOCH ═ CH₂or-OCOCCH₃＝CH₂，

a is 0-10, b is 1-30, c is 1-30.

2. A compound according to claim 1, characterized in that R₁Is Cl.

3. A compound according to claim 1, characterized in that R₁Is CF₃。

4. A compound according to claim 1, characterized in that X and Y are F; or X is F and Y is Cl; or X and Y are hydrogen.

5. A compound according to claim 1, characterized in that a is 0 to 5.

6. A compound according to claim 1, characterized in that c is 1; and R is₂And R₃Is H or CH₃。

7. A compound according to claim 1, characterized in that c is 2; and R is₂And R₃Is H or CH₃。

8. A compound according to claim 1, characterized in that R_FIs a polyfluoroalkyl group having 1 to 3 fluorinated carbon atoms.

9. A compound according to claim 1, characterized in that R_FIs a polyfluoroalkyl group having 4 to 16 fluorinated carbon atoms.

10. Compound according to claim 1, characterized in that the compound of formula 1 has a molecular weight of more than 750 g/mol.

11. A compound according to claim 1, characterized in that a + b > 3.

12. A copolymer comprising a monomer of formula IV, one or more non-fluorine containing polymerizable vinyl monomers, one or more thermally crosslinkable or isocyanate reactive monomers, and optionally a chlorine containing polymerizable vinyl monomer.

13. A copolymer comprising, by total weight of the copolymer:

a) from 20% to 97% by weight and preferably from 40% to 90% by weight of monomers of formula IV wherein Z is-OCOCH ═ CH or-OCOCCH₃＝CH，

b) From 0% to 80% by weight and preferably from 10% to 50% by weight of one or more non-fluorine-containing polymerizable vinyl monomers, and/or

c) From 0.5% to 20% by weight and preferably from 1% to 10% by weight of one or more thermally crosslinkable or isocyanate-reactive monomers.

14. A copolymer comprising, by total weight of the copolymer:

a) from 40% to 90% by weight and preferably from 45% to 85% by weight of monomers of formula IV wherein Z is-OCOCH ═ CH or-OCOCCH₃＝CH，

b) From 0% to 50% by weight and preferably from 0.01% to 30% by weight of one or more non-fluorine-containing polymerizable vinyl monomers, and/or

c) From 0.5% to 20% by weight and preferably from 1% to 10% by weight of one or more thermally crosslinkable or isocyanate-reactive monomers, and

d) from 0.5% to 50% by weight and preferably from 2% to 30% by weight of chlorine-containing polymerizable vinyl monomers.

15. Use of the copolymers according to claims 12 to 14 for oil-, water-and dirt-repellent finishing of fibrous substrates.