TW200808835A - Fluorous telomeric compounds and polymers containing same - Google Patents

Abstract

Claimed are fluorous telomeric compounds of the formula RF-A-CXY-Z (IV) where RF is a perfluoroallkyl radical of 1 to 20 carbon atoms, A is a group of the formulae Z is CH2OR3, or COO¯ 1/q Mq+ or CON(R4)R5OR3 X and Y are H, Cl or F R1 is CF3, OR2, Cl, Br or I, R2 is perfluoromethyl, perfluoropropyl or perfluoropropyloxypropyl R3 is H or COCR6=CH2 R4 is H or alkyl of 1 to 6 carbon atoms R5 is allkylene of 1 to 13 carbon atoms R6 is H or CH3 M is H or a metal cation or an ammonium cation or a substituted ammonium cation q is the valency of M a is from 0 to 10 and b is from 1to 30. These compounds are copolymerized with further monomers. The copolymers thus obtained are useful for water-, oil- and soil-repellent finishing of fibrous substrates.

Description

200808835 Nine, invention description: [Prior Art] Each fluorine compound is often used as a surfactant or a wetting agent, and is widely used for surface treatment of a substrate. It has been found to be commonly used for the oil repellent, water repellent and soil repellent surface processing of fibrous substrates such as carpets, textiles, leather products, non-wovens and paper, and hard substrates such as wood, metal or concrete. The substrate thus treated is reduced in the inhalation of hydrophilic or hydrophobic liquids and promotes the removal of existing contamination. For example, perfluoroalkyl iodide obtained via telomerization of a telogen with a fluorinated monomer such as tetrafluoroethylene is an important starting point for the preparation of fluorochemicals. Unpublished German Patent Application 1 〇 2006 〇〇 1 218.6 describes a rat-containing telomer compound of the formula:

Rf-A-[CH2]cCR2R3-Z wherein Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, and A is a group of the formula -CF-CF L 丨- a CFrCXY : or a -CFrCXY- - CF; -CF - R1 - - b L j" R is CF3, 〇R4, Cl, Br or I, R2 and R3 are fluorene, alkyl or aryl, and R4 is perfluoromethyl, perfluoropropyl or Perfluoropropoxypropyl, X and Y are Η, C1 or F, Ζ is -OH, _ococh=ch2 or _ococch3=ch2, a is 0 to 10, b is 1 to 30, and c is 1 to 30. . 121132.doc 200808835 For use as a surface modifying material, perfluoroalkyl iodides are typically first converted to perfluoroalkylethyl iodide with ethylene. The perfluoroalkylethyl iodide can then be converted to the corresponding perfluoro-phenethyl alcohol in a suitable state. Next, the corresponding (f-based) acrylate monomer of Formula 1 can be prepared from perfluoroalkyl alcohol.

RfCH2ch2OCOCR=CH2 (I) It is known from the various derivatives of acrylic acid and methacrylic acid to prepare fluorine-containing acrylates and methacrylates according to formula I, respectively. The copolymer prepared from such a fluorine-containing acrylate is particularly suitable for use in a modified table.

Make /, oil, water and soil repellent to, for example, surface finish textiles or coated leather products and paper. A A fluorinated monomer of the formula known for similar applications. RFS 〇 2 NR, (CH 2 ) n 〇 COCR = CH 2 (11) The fluorinated alkyl sulfonic acid fluorine compound used for the synthesis thereof is obtained by electrochemical fluorination. It has been determined that for both monomer types (1 and „), the surface is coated with a longer and rationally linear perfluoroalkyl chain consisting of a fluorinated carbon atom to give a particularly low surface energy. Fluorine-containing compounds having a linear perfluoroalkyl chain containing 8 deficient carbon atoms, including the monomers described above, are degradable to form a fully octyl carboxylic acid and a perfluorooctyl acid, respectively. The product, the listener does not degrade further, and therefore it is stable. Furthermore, it is believed that such human spores accumulate in living organisms. ', Therefore, in recent years, various proposals have been made for environmentally acceptable production. a compound. Fluoride 121132.doc 200808835 W〇02/16306 describes a branched fluorine-containing (meth) acrylate having the formula III,

Rf(Rf,)CH〇COCR=CH2 (III) having a linear or branched perfluoroalkyl Rf having 5 or less carbon atoms and a branched perfluorocarbon having 3 to 5 carbon atoms Alkyl chain Rf'. These compounds in particular lead to degradation products of low molecular weight and low toxicity. It is known that shorter chain perfluoroalkylsulfonic acid derivatives are more easily eliminated from the body of living organisms. WO 03/062521 describes a textile surface treatment based on a perfluorooctane sulfonic acid derivative in accordance with formula II: RFS02NR'(CH2)n0C0CR=CH2 (II) The perfluorobutylsulfonate The acid derivative has a partially branched perfluoroalkyl group having 4 fluorinated carbon atoms, n = 1, 2, and R' = H, an alkyl group, and R = H, CH3. a compound having a fluorinated alkyl group having 4 carbon atoms and conforming to formula I is described in EP 1 632 542 A1,

RfCH2CH2OCOCR=CH2 (I) Degradation products may be more easily eliminated from living organisms. WO 02/34848 describes the use of trifluoromethyl or pentafluoroethyl as a perfluoroalkyl-based polypropylene oxide. Such compounds are also indicated as fluorosurfactants or environmentally acceptable perfluoroalkyl-containing compounds for coating. WO 2004/060 964 describes fluorinated polyethers having a molecular weight of more than 750 g/mol, which are especially susceptible to elimination in vivo from living organisms. WO 03/100 158 describes the use of such alcohols and acrylates for surface processing textiles. However, the proposed exposure to the environmentally friendly alternatives to perfluoroalkyl compounds to date has been less effective than the use of such compounds as the basis for oil and water repellent surface processing. 121132.doc 200808835. This is reflected in achieving water and oil repellency and coating durability. SUMMARY OF THE INVENTION One object of the present invention is to provide a substitute for a polyfluoroalkyl-containing compound and a derivative thereof which has no bioaccumulation effect. Its performance profile further includes its effectiveness when used for oil and water repellent coatings. In addition, these compounds must remain processable on an industrial scale.

Polyfluoroalkyl compounds as defined below have been found to surprisingly result in oil and water repellent coatings with high efficiency and durability, as well as being environmentally compatible. Accordingly, the present invention provides fluorine-containing carboxylic acids and/or fluorine-containing alcohols and derivatives thereof having a molecular weight of more than 75 〇 g/m 〇1. The present invention further provides a fluorine-containing compound which is composed of a polyfluoroalkyl chain which is partially branched and has a linear chain, and which has a lower temperature than melting of an equal molecular weight composed of a linear polyfluoroalkyl chain. Melt at the temperature. The invention further provides fluorocarboxylic acids, carboxylates and ester derivatives prepared by the corresponding polyfluoroalkylalkyl groups. The present invention provides a fluorine-containing telomer compound of the formula IV:

Rf-A-CXY-Z (IV) wherein RF is an all-gas group having 1 to 20 carbon atoms, and A is a group of the formula: CF.-CF I - R1 -CFrCXY· or CF-CXY- Z Is CH2〇r3 or c〇0_ 1/q Mq+ or C0N(R4)H50R3, 121132.doc -10- 200808835 X and Y are Η, Cl or F, R1 is CF3, OR2, Cl, Br or I, R is Perfluorodecyl, perfluoropropyl or perfluoropropoxypropyl, R3 is hydrazine or COCR6 = CH2, R4 is hydrazine or an alkyl group having 1 to 6 carbon atoms, and R5 is 1 to 13 carbons The alkyl group of the atom, R6 is hydrazine or CH3, Μ is 11 or a metal cation or an ammonium cation or a substituted ammonium cation, q is a valence a of 0 to 10, and b is 1 to 30. Preferred are fluorochemicals having a molecular weight greater than 750 g/moli SIV. In particular, it is preferred that the compound has a molecular enthalpy of more than 1 〇〇〇 g/m〇l. The poly-mole alkyl group RF may be a mixture of a polyfluoroalkyl group having a single chain length or a polyfluoroalkyl group having a different chain length (CF3 C2F5, C3F7, c4F9, c6F", CiF2, a group). Polyfluorocarbon

The base can be branched or unbranched. More L is a compound of the present invention having a saturated poly-I-base b having a chain length of from 1 to 20 fluorinated carbon shoulders + R ^ ' & atom and comprising at least one terminal cf3 group. The complete fluorination of the soil is particularly preferably one to three or four to sixteen carbon fluorides of the original carbon chain RF. X and Y may independently be Η, ri + v ^ . γ... and ¥ are preferably fluorine atoms. Alternatively, X is a gas atom, and gamma yoke is a ruthenium atom, or X and ruthenium are hydrogen atoms. a is preferably from 〇 to 1〇, and more preferably from 〇 to 5. 121132.doc 200808835 b is preferably 1 to 3 〇, and more preferably a+b>3. The functional group Z is a carboxylic acid, a carboxylate, a carboxamide, a (meth)acrylic acid carboxylic acid alkyl ester, an alcohol, a methacrylate or an acrylate. R is a group having a large volume of space on the polyfluoroalkyl chain which inhibits crystallization. Particularly preferred is a perfluoromethyl group, a perfluoroalkyl ether group or a chlorine atom, a bromine atom or an iodine atom. The perfluoromethyl group is the best. R2 is preferably a perfluoromethyl group, a perfluoropropyl group or a perfluoropropoxypropyl group. The perfluoro fluorenyl group is the best. R3 is hydrogen or cocr6=ch2. R4 is hydrogen or an alkyl chain having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group. R5 is an alkylene chain having 1 to 13 carbon atoms, preferably an ethyl group. R6 is hydrogen or methyl. The compounds of the invention are prepared from the corresponding polyfluoroalkyl iodides in the evenings and in the process. In the first step of the process (called the telomerization reaction), it is at 2 Torr. 〇 to 25〇, under the free radical formation mechanism, a fluorine-containing compound (polymerization agent) capable of transferring a radical chain is reacted with at least one fluorinated monomer (backbone) to form a telomer of the following formula: The telogen includes a calcined composition having a radically separated group, such as a fluorene-containing, a fluorine-containing thiol, a fluoroalkylthiol, a fluoroalkyl sulfide, and a fluorine-containing alkyl alcohol. It is preferably a mixture of a perfluoro-based iron having a single-chain length or a perfluorodecyl group having a different chain length. Perfluoroalkyl; branched or unbranched, for example, all-", perfluoroethylene, n-perfluoro? 121132.doc 200808835 iodine: isoperfluoropropyl iodide, n-perfluorobutyl iodide, isoperfluoro Isomers such as butyl iodide, H-filled and perfluorohexyl moth, perfluorooctyl-filled, perfluorodecyl-filled, and fluorescein-doped. Preferably, the invention has 1 to 2 〇. The chain length of the carbon atom and at least one perfluoroalkylene group of the terminal CF3 group. The w is preferably a chain length and an average of about 6 to 16 fluorinated carbon atoms or 8 to 6 fluorinated carbon atoms. 7.5 Dunhua carbon atoms or about 9 Dunhua carbon atoms, #长_methyl-hard, all-gas ethyl eu, perfluoropropyl-breaking or all-gas isopropyl iodine or various perfluoroalkyl breaking technology The mixture is added to the telomer. The higher molecular weight is gradually formed. In contrast, it depends on which of the following three variants is selected. In the first variant, only the fluorinated unsaturated monomer CFpCFL is initially added to the oligomer, followed by the telomerization reaction conditions. Product addition / CF2-CXY monomer. The telomer thus obtained has the formula r

Rf—CF2CF——CF^CXY— I - I _ a - - b

FT and show that the monomers are incorporated on a block by block basis. In the younger body of wheat, only the fluorinated unsaturated monomer CF2=cxy was initially added. The product is then added to the monomer of formula cf2 = CFRi under telomerization conditions. The resulting telomer 121132.doc -13· 200808835

Rp—CF^CXY---CFj—CF--1 - ”bL I Ja R1 also” refers to the incorporation of monomers by block, but the monomers are added in reverse order. In the second variant, two singles Simultaneous addition of a mixture of the monomers results in a random incorporation of the monomer CFfCFRicj^cxY. Examples of compounds of the formula CFrCFR are chlorotrifluoroethylene, bromotriethylene, iodotrifluoroethylene, perfluorodecyl vinyl ether, perfluoroethylene. Vinyl ether, perfluoropropyl vinyl ether, perfluoropropoxypropyl vinyl ether, and terminally double-bonded knives and non-fluorinated hydrocarbons such as hexa-I propylene, perfluoro butyl sulphate, and perfluoro Hexene or perfluorooctene. Examples of the compound of formula CF2=CXY are, for example, tetrafluoroethylene, vinylidene, fluorene trifluoroethylene, trifluoroethylene, i-difluoroethylene, and L-chloro-2,2- Difluoroethylene. In the case of an iodine-containing compound, the free radical that initiates the telomerization reaction can be generated by a source of free radicals. Suitable sources for the formation of free radicals include light or heat. The source is usually in the infrared to ultraviolet. The zone has a maximum value. The radical formation due to heat usually occurs at a temperature between 1 〇〇 and 〇 25 〇. Suitable sources for the formation of free radicals further include chemical radicals which are capable of reducing the reaction temperature required for free radical formation to enthalpy. Between 〇 and bot, such as organic or inorganic peroxides, azo Compounds, organic and inorganic metal compounds and metals, and combinations thereof, are particularly preferably persulfated 1-fluorinated and unfluorinated organic peroxides, azo compounds and metals such as RU, Cu, Ni, Pd and Pt. 121132.doc -14- 200808835 The telomerization reaction can be carried out in the absence of a solvent, in a solvent, in a suspension or in an emulsion. The reaction without a solvent or in an emulsion is particularly preferred. In the case of an emulsion, the telomer is reacted. First, it is converted into an aqueous emulsion with the help of the surfactant. It can be stabilized by anionic, cationic, non-ionizing + nonionic or amphoteric surfactants and combinations thereof. For example, including the double and the mouse interface The active agent is especially suitable. The reaction usually takes place at elevated temperatures via the addition of a main chain and a free radical initiator. Additional components can increase the reaction yield, for example a small amount of sulfite, chlorite or dithionite. The aqueous solution is then converted into a polyfluoroalkyl carboxylic acid of the formula ιν (Z=COOH) via the telomerization reaction.

Rf-A-CXY-Z (IV). Various preparation methods can be used for the oxidation to poly-alkyl sulphuric acid. One of the reactions described in DE 3 〇 43 249, for example, is included in hydrazine. The poly(alkyl iodine) is oxidized with fuming sulfuric acid to form a polyfluoroalkyl carboxylic acid at a temperature of 丨8 〇. By reacting a polyfluoroalkylcarboxylic acid with a base such as lithium hydroxide, sodium hydroxide, hydroxide, hydrogen peroxide, barium hydroxide, hydrogen peroxide or tetrabutylammonium hydroxide, wherein Z = C00- 1/qMq+ of formula IV polyoxyalkylcarboxylate. Polyalkylene tetamine is used as a starting material for the preparation of various alcohols of the formula IV (Z=CH2OH and z=C0N(R4)R50H). In the first embodiment, it is at 150 to 220 in the presence of a suitable catalyst and hydrogen as described, for example, in DE 22 22 682. The polyfluoroalkylcarboxylic acid is hydrogenated at a temperature to form a 1H,1H-polyfluoroalkyl alcohol (Z ==CH2〇H). A metal and a metal oxide catalyst are preferred. A rhodium catalyst is particularly preferred.

In the second embodiment, by using a polyfluoroalkylcarboxylic acid with an amino alcohol 121132.doc -15 · 200808835 =: guanamine. This reaction can be carried out under solvent or solvent-free conditions. The amine amino alcohol can be a first amino alcohol, #土乙知, 3' propyl alcohol, 4-aminobutyl alcohol, 2, yl] butyl 4-methylamine 2-methylamine 3-ethyl Amine 5-ethylamine 2-propylamine:: amino sterol, 2, pentyl alcohol, 6 • aminohexanol; or a second amino alcohol such as “ylaminoethanol, 3-methyl Aminopropanol butanol, 2-methylaminobutanol, 5-nonylaminopentanyl-1-indanol, 6-methylaminohexanol, 2-ethylaminoethanol Propyl alcohol, 4-butylaminobutanol, decylethylamino 丨-butanol pentanol, 2-ethylamino-indole pentanol, 6-ethylaminohexanolethanol, 3 -propylaminopropanol, 4-aminobutanol, propyl propylaminobutanol, 5-propylaminopentanol, 2-propylamino group _: pentanol, 6-propylamino group Hexyl butylaminoethanol, 3-butylaminopropanol, 4-butylaminobutanol, 2-butylamino-1-butanol, 5-butylaminopentanol, 2-but Further, amino-aminopentanol and 6-butylaminohexanol are particularly preferably 2-aminoethanol, hydrazine methylaminoethanol, 2-ethylaminoethanol, and 3-propylaminoethanol. 1H, 1H-polyfluoroalkyl alcohol and polyfluoride obtained by the method Carboxylamamine can be reacted with (meth) acrylate, acid or decyl chloride to form the corresponding fluorine (meth) acrylate having the formula: rf-a-cxy-ch2ococr6=ch2 and

Rf.A_CXY-CON(R4)R5OOCOCR6=CH2. The reaction with the (meth) acrylate sulfhydryl gas is usually carried out in the presence of a test such as triethylamine to combine the formed hydrogen chloride. Suitable catalysts (e.g., tin catalysts) are useful for transesterification. 121132.doc -16- 200808835 These acrylates and methacrylates may be thermally crosslinkable with fluorine-free polymerizable vinylic monomers and/or chlorine-containing polymerizable vinylic monomers and, as appropriate, one or more The isocyanate-reactive monomer is copolymerized. The present invention also provides a copolymer of the following materials (based on the total weight of the copolymer) a) 20 wt% to 97 wt% and preferably 40 wt% to 90 wt% of the monomer of formula IV, wherein Z is CH2OCOCR6=CH2 or con(r4)r5o〇cocr6=ch2, b) 0 wt% to 80 wt% and preferably 10 wt% to 50 wt% of one or more non-fluorine-containing polymerizable vinyl monomers and/or Or c) from 0.5 wt% to 20 wt% and preferably from 1 wt% to 10 wt% of one or more heat-crosslinkable or isocyanate-reactive monomers. The invention further provides copolymers (based on the total weight of the copolymer) comprising: a) from 40 wt% to 90 wt% and preferably from 45 wt/〇 to 85 wt% of the monomers of formula IV, wherein Z Is CH20C〇CR6=CH24C0N(R4)R50〇C〇CR6=ch2, b) 0 wt% to 50 wt% and preferably 0·0 1 wt% to 30 wt% one or more of fluorine-free polymerizable ethylene Monomer and/or c) 0.5 wt% to 20 wt% and preferably 1 wt% to 10 wt% of one or more heat-crosslinkable or isocyanate-reactive monomers and d) 0·5 wt% to 5 0 wt% and preferably 2 wt% to 30 wt% of the chlorine-containing polymerizable vinyl monomer. The optional comonomer (b) is not meant to be (not containing fluorine) and is represented by a variety of commercially available propane-bakes 121132.doc -17- 200808835 acid esters and mercapto acrylates and styrene derivatives. Examples of unvaporized comonomers are hydrocarbyl esters and decylamines of unsaturated carboxylic acids. These include, for example, acrylic acid, methacrylic acid, cyanine acrylic acid, croton, maleic acid, fumaric acid and the following esters of itaconic acid and guanamine: vinyl, allyl, methyl Base, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 3,3-dimercaptobutyl, heptyl, octylisooctyl, eleven alkyl , hexadecyl, stearyl, 222, hexyl, fluorenyl, isobornyl, phenyl, benzyl, adamantyl, tolyl, (2,2-dimethyl And 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 hexadecyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether and ethyl vinyl ether; ~ Bu not # nitrile such as acrylonitrile, methacrylonitrile, α-chloride Acrylonitrile, α-cyanoethyl acrylate; aminoalkyl (meth) acrylate, such as ruthenium (mercapto) acrylate, ruthenium-diethylaminoethyl ester, (meth)acrylic acid Butylaminoethyl ester; alkyl (meth)acrylate having an ammonium group, such as 2-methacryloxyethyltrimethylammonium chloride; styrene and its derivatives, such as vinyl toluene, Α-methyl stupid ethylene, heart cyanomethyl styrene, chloromethyl styrene; olefins such as ethylene, propylene, isobutylene, butadiene, isoprene; and methoxy polyethylene glycol (A) Base) acrylate. Particularly preferred optional comonomers (b) may be the following esters or decylamines of acrylic acid and methacrylic acid: methyl, ethyl, propyl, butyl, 121132.doc -18- 200808835 Base, 2-ethylhexyl, tetradecyl, dodecyl, octadecyl, decyloxy poly(ethylene glycol) and decyloxy poly(propylene glycol). The comonomer (c) contains one or more crosslinkable groups. The crosslinkable group is a functional group capable of being added to the reaction with the substrate and/or with another polyfunctional compound added. The crosslinkable groups may be: a carboxylic acid group, an ethylenically unsaturated group, a trans group, an amine group, an N-alkyl alcohol decylamino group, an isocyanate group or a protected isocyanate SI group. Examples of comonomers having one or more crosslinkable groups include unsaturated carboxylic acids and acrylic acid, methacrylic acid, alpha-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, and itacon An acid anhydride, including a monomer such as hydroxyethyl (meth) acrylate and hydroxypropyl methacrylate, hydroxybutyl (meth) acrylate, poly(ethylene glycol) mono (fluorenyl) Acetate, poly(propylene glycol) mono(meth)acrylate, poly(ethylene glycol)-co-poly(propylene glycol) mono(meth)acrylate, polytetrahydrofuran mono(indenyl)acrylate, Ν-Hydroxymethyl (meth) acrylamide, hydroxybutyl vinyl ether. Other crosslinkable monomers are, for example, vinyl (meth)acrylate, allyl methacrylate, fluorenyl-methoxymethylpropenylamine, hydrazine-isopropoxymethyl propyl amide , Ν-butoxy propyl amide, Ν-isobutoxymethyl propyl decylamine, glycidyl (mercapto) acrylate and α, _-dimethyl-isopropyl isopropyl isocyanate Benzo vinegar. Further examples are the release of isocyanate g under high temperature or light irradiation, for example, an isocyanate terminated (mercapto)alkyl acrylate protected by phenol, ketone oxime and pyrazole. The optional comonomer (d) contains gas. Examples of chlorine-containing comonomers are halogenated hydrocarbons such as vinyl, vinylidene chloride, 3-air-1-isobutylene, chloroprene-, 1,1-one-butadiene and 2,5-di Methyl-1,5-hexane dilute. Ethylene 121132.doc -19- 200808835 Chlorine and vinyl chloride are particularly preferred alternative comonomers (d) The comonomers described herein are typically prepared by free radical polymerization techniques, for example by solvents, emulsions. Prepared by microemulsion or miniemulsion polymerization techniques. Variants of emulsion polymerization are especially preferred. The emulsion polymerization of the monomers occurs in the presence of water, a surfactant, and an optional organic solvent. The mixture can be pre-emulsified prior to polymerization by means of a high homogenizer or the like. The polymerization is usually carried out in the presence of a free radical (10) agent at a temperature between 50 ° C and 15 Torr. A variety of anionic, cationic, nonionic or zwitterionic surfactants can be used alone or in combination. Examples of nonionic surfactants include poly(ethylene glycol) lauryl ether, poly(ethylene glycol) tridecyl ether, poly(ethylene glycol), and poly(ethylene glycol). _Co-poly(propylene glycol) hexadecane bond, poly(7): alcohol) stearyl hydrazine _, poly (ethylene glycol) oil county ether, poly (ethylene glycol) decyl ether, poly (ethylene glycol ) octyl _, poly (ethylene glycol) monododecanoic acid vinegar, poly (ethylene glycol) monostearic acid vinegar, poly (ethylene glycol) monooleic acid vinegar, sorbitan mono-sour vinegar, Sorbitan monostearate, sorbitan monosuccinic acid, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate Vinegar's dehydrated sorbitol trioleate, = ethylene glycol) sorbitan monododecanoic acid, poly(ethylene glycol) dehydrated mountain = early vinegar, poly(ethylene glycol) sorbitan Alcohol monostearate, mono(ethylene glycol) sorbitan monooleate, poly(ethylene glycol)_co-poly(propanol: alcohol), polyglycerol fatty acid ester, modified with polyether Oyster oil and perfluoroalkylation Acetate adduct. Relative to the weight of the polymer, the county + in which the non-interface active sword is used is in the range of 〇·1 Wt/ο to 100% by weight. An example of a cationic interface-active sword of the present invention is an ammonium compound based on saturated and unsaturated 121132.doc -20- 200808835 fatty acid amines, such as octaacetic acid, octadecyl dimethyl chlorinated; An ammonium compound of a polyethoxylate and a polypropoxide and an interpolymer thereof, such as polyoxyethylidene monomethylammonium chloride; an ammonium compound based on an arylamine such as biphenyltrimethyl Ammonium chloride, imidazoline derivatives, such as ammonium salts formed by automatic lipids and imidazolines, cationic surfactants based on polyoxygen oxides, and cationic surfactants based on fluorine. The amount of the cationic surfactant used is in the range of from 0.1% by weight to 100% by weight based on the 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; alkylsulfonates such as dodecylsulfonic acid. Sodium; alkyl benzene sulfonate, such as nonylphenol ether sulfate, sulfosuccinate, such as sodium hexaether sulfosuccinate; fatty alcohol squarate, such as dodecapine acid steel; And fatty acid salts, such as sodium stearate. The amount of the anionic surfactant used is in the range of 〇·; wt% S1 〇〇 wt% relative to the polymer". Examples of free radical initiators are organic or inorganic peroxides, azo compounds, organic and inorganic metal compounds and metals, and combinations thereof. It is better to: nitrite t such as azobisisobutane _N, azo bismuth and azo-(2-cyanovaleric acid), 2, 2, and argon Monomethylpropane) dihydrochloride, hydrazine peroxide, such as hydroperoxide ^ cumene cumene, tert-butyl hydroperoxide and hydrazine tert-butyl peroxide, peroxy-deuteration - Alkyl (such as dibutyl peroxide and dicumyl peroxide), premature U 匕酉曰 (such as tert-butyl perbenzoate and peroxy o-dibenzoic acid second third @ ^ mj転), bismuth peroxide base (such as over-emulsified methacrylate and ruthenium oxyhydroxide); machine over-halide, such as 121132.doc 200808835 ammonium sulfate and potassium persulfate; and these designated compounds with organic or A combination of an inorganic metal compound and a metal. Chain transfer agents can be used in polymerization orders such as alkanethiols. Examples of organic solvents in solvent and emulsion polymerization are: ketones such as lactone, methyl ethyl ketone and methyl isobutyl ketone; alcohols such as ethanol, isopropanol and butanol, polyols such as 13_d2 Alcohol, i,6-hexanediol, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and glycerol; the more the polyol and the ester, such as dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, triethylene glycol Monomethyl ether and diethylene glycol monobutyl ether acetate; esters such as ethyl acetate, propyl acetate, butyl acetate, dibutyl adipate and dibutyl succinate; hydrocarbons and functional hydrocarbons 'such as toluene, diterpene, octane, whole gas and U dichloro-2,2,3,3,3-pentafluoropropene. The preferred solids content of the prepared polymer dispersion is between 2 Torr and 仂 wt%. A fluorocopolymer containing a fluoromonomer of formula IV (2 is CH2〇c〇CR6=cH2 or CON(R4)R5〇〇COCR6=CH2) suitable for materials (such as carpets, textiles, leather goods, non-woven goods or The paper is coated with a substrate such as wood, metal or concrete. The copolymers impart water, oil and soil repellency properties to the substrates. Accordingly, the present invention also provides for the treatment of fibers with an effective amount of an aqueous dispersion containing I. Method of Substrate The content of the formulation of the present invention for surface-treated textiles and other sheet-like structures is selected to transfer sufficient repellent properties to the substrate to be treated. And the surface processed sample to determine the amount of wet coating. Straw 121132.doc -22- 200808835 The fluorine-containing textile surface processing agent can be used together with other additives & including water-repellent substances (such as wax, poly Oxygen, antimony compound or stearate) and other oil repellent substances, surfactants, #insecticides, flame retardants, antistatic additives, plasticizers, fixing agents and anti-wrinkle additives, these In order to not be weakened to textiles and The stability of the composition can be cross-linked by the addition of a reactive additive such as a melamine resin, a protected isocyanate or an epoxide to the fluorine-containing textile surface treating agent of the present invention. The fibrous substrate can be, for example, carpet, textile-, leather, non-woven, and paper. & etc., especially from natural fibers (such as cotton, linen, and silk), synthetic fibers (such as polyamide, polyester, polyamine). Carbamate, polyolefin, poly(methyl) acetoacetate, poly(ethylene), poly(vinyl alcohol), semi-synthetic fibers (such as human cotton or acetic acid), inorganic fibers (such as fiberglass) Or any desired combination of specified fibers 5 or a woven product of the specified fibers, such as 陶 纤维 fiber or Α, etc. For coating, the substrate is usually impregnated with a copolymer and optional additives. a dilute dispersion towel. Alternatively, the dilute dispersion can be applied to the substrate. The impregnated substrate is then extruded by a reel system to remove excess dispersion, dried in an oven, and sufficient to ensure Cross-linking on treated substrates Crosslinking at temperature is sufficient to ensure crosslinking time on the substrate being treated. This crosslinking process is typically carried out at a temperature between 5 Torr and about (10). Generally, at about 120 C to 180 ° C The S degree and especially about 13 (the time from rc to the temperature of from 2 sec to 1 pm is appropriate, preferably from 5 seconds to $ minutes. 121132.doc -23- 200808835 Coating the formulation to the base Another alternative is a foam coating with a mouth. It is applied to the substrate in a foamy form, and the connector is dry and crosslinked. The foam is coated with a lacquer, and the formulation is usually with an additional 4 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Hang 3 has Ada 20 Wt% of the fluorine

For the textiles, the - 士 - T 仲, 目, ^ surface processing 'can be used in the specific job before and after washing the sputum "test water repellency, isopropyl alcohol and oil repellency properties. According to AATCC standards The test method and the bad water test were used to obtain the water repellency. The 4 distilled water was sprinkled onto the spun _, ,, ..., the mouthpiece substrate to be tested, and then the evaluation described in the test method was given. Un., ^, and visually compare the type of wetting to produce a numerical value. After spraying with water, the reported Zhao Bo also * meaning (Table 1): The value of the surface is related to the appearance and has the meaning of the water in the table 1 Surface wet main jj^L surface part of the wet surface is completely wet _: column water - isopropyl alcohol test solution for the second test can be used to test the substrate's isopropyl alcohol resistance is called the highest level of ιρα reported = solution: where the fabric does not wet within 10 seconds and the droplets still have a spherical or sigma shape. The wetting substrate or the material that rejects only 1 GG% water (G% isopropanol) (i.e., the minimum wetting test solution) has a rating of 〇, while the substrate that rejects isopropyl _ water has a rating of 10. Intermediate levels can also be specified. 121132.doc •24- 200808835 Root::Standard test method 118, reject (four) Sex: ... force, a higher level within the evaluation range indicates better rejection of the / wood, especially oily liquids. The test droplets in the normalization (consisting of a series of hydrocarbons having a different surface tension of 7 k by careful aspiration) are applied continuously to the surface of the sample to be tested, and in the specified contact Visually assess the wetness after time. The oil repellency value corresponds to the highest number of test liquids which did not cause surface wetting. The standard measurement outside, the right thief 曰 + know + move 5 type liquid has the following composition (table: Table 2

Zhuang Si Nujol is a mineral oil from p1〇ugh Inc., which is at 38. The underarm has a viscosity of 3 60/390 plug (3叮1;) 〇1〇 and at 15. The armpit has a specific gravity of () 88〇/〇.9〇〇. The prior art FC polymer currently gives a 6 oil repellency value; it is often considered that grade 5 is already excellent. EXAMPLES The following examples are intended to illustrate the subject matter and advantages of the present invention, and the materials and amounts cited in the examples are not to be considered as limiting. Synthesis 121132.doc -25- 200808835 Example 1: Synthesis of C8F17(CF2CF(CF3))a(CF2CF2)bI 11 〇g(〇18 m〇1)Fiu〇wet 1812 was prepared by vigorous stirring at 60 °C ( Clariant), 15 g of Fluorolink C (Solvay Solexis), an emulsion of 5 g of ammonia and 90 g of water, and which was introduced into the autoclave together with 2.5 g of ammonium persulfate as starting feed. The purification was repeated with nitrogen after the pressure test. During the stage of heating to 80 C, hexafluoropropylene and tetrafluoroethylene were added to the stirred emulsion at a total pressure of up to 17 bar at a ratio of 3:5. The pressure was maintained at P bar until 82.5 g (〇.55 mol) of hexafluoropropylene and 90 g (〇.9〇 m〇1) of tetrafluoroethylene were added. After the pressure was lowered, the autoclave was cooled to room temperature, and the fluorine-containing compound phase was separated by adding a force: salt, and washed. The low molecular weight component is separated by distillation. The 11.2% iodine content indicates an average molecular weight of about 14 〇〇 g/m〇1

Perfluoroalkane

Fluorolink C is a perfluoropolyether acid. Examples 2 to 9: Synthesis of Polyfluoroalkyl Iodine

2 to 9). Synthetic junctions 121132.doc -26- 200808835 are shown in Table 3. Table 3 telomerization reaction to prepare polyfluoroalkyl iodide CFrCFCt which is composed of ~fT, $m, and the following general composition

R-* self-iodine content determination ** expressed as Fluowet 1612 and Fluowet 1812 compounds are self

Clariant's perfluoroalkyl iodide mixture, each having from 6 to 14 carbon fluoride atoms, each having an average chain length of about 7.5 fluorinated carbon atoms and 9 fluorinated carbon atoms. Example 10: Synthesis of C8F17(CF2CF(CF3))a(CF2CF2)bCF2COOH Weighed 146.5 g (〇.11 m〇l) from the polyfluoroalkyl iodide of Example 1, 21 g of zinc sulfate and 105.5 g of fuming sulfuric acid ( 65% S03) to the shaker autoclave and reacted at 155 C for 8 hours. After the reaction, the reaction mixture was cooled and mixed with 1,1, 1,3-ethane. After the shock, the light phase was separated and carefully hydrolyzed with warm water. Repeat washing with warm water to leave 11〇·7 g(〇· 10 m〇l) polyfluoroalkyl tetamine 0

The acid value was 48.9 mg KOH per gram of the product 121132.doc -27-200808835 Examples 11 to 18: Synthesis of polyfluoroalkylcarboxylic acid Example 10 was repeated to prepare the corresponding polyfluoroalkylcarboxylic acid (Examples 11 to 18). The results of the synthesis are shown in Table 4.

Example 19: Synthesis of C8F17(CF2CF(CF3))a(CF2CF2)bCF2CH2OH 2.0 g of Η101 B/W 钌 catalyst (Degussa) and 90.2 g of polyfluorononyl carboxylic acid from Example 10 were initially fed under nitrogen. Material introduction. After a 5 Torr nitrogen pressure test, 40 bar of hydrogen was injected. The reaction mixture was maintained at 14 (rc for 2 hours). After decompression, the product was filtered at 70 ° C, washed with hot water, and volatile components were removed to obtain 85 g of polyfluoroalkyl alcohol. The gram product is 46.7 mg KOH.

Example 20 · Synthesis of C8F17 (CF2CF(CF3)a(CF2CF2)bCF2CON(CH3)CH2CH2OH 60% of the polyfluoroalkylcarboxylic acid from Example 1 was fed to a 25 〇... four-necked flask. 15·4 g of amino-aminoethanol was added with stirring over a period of 30 minutes. The reaction mixture was slowly heated to 18 Torr. The formed water was removed via a Dean-Stark apparatus. The reaction mixture was stirred at this temperature for an additional 4 hours to carry out a supplementary reaction. The reaction mixture was cooled to 7 ° C, combined with water and precipitated in water, and washed with 150 ml of ethanol pre-heated and dried. 83.7 g of polyfluoroalkylguanamine OH value 48 2 mg κ 每 per gram of product. Examples 21 to 24 · Synthesis of polyfluoroalkyl alcohol Example 19 was repeated to prepare the corresponding polyfluoroalkyl alcohol (Examples 21 to 24) The results of the synthesis are reported in Table 4. 121132.doc -28- 200808835 Examples 25 to 28: Synthesis of Polyfluoroalkylguanamine The Example 2 was repeated to prepare the corresponding polyfluoroalkylguanamine (Examples 25 to 28). The synthesis results are reported in Table 4. Example 29: Synthesis of C8F17(CF2CF(CF3)a(CF2CF2)bCF2CH2OCOCH=CH2 80·1 g of alcohol from Example 19, 23.5 g of acrylic acid, 〇.3 g of methanelithic acid and 〇.4 g of p-methoxyphenol were fed into a three-necked flask, and the starting feed was heated to 8 〇. °C. The reaction water was separated at a reaction temperature and a pressure of 2 mbar over 24 hours during the reaction. The organic phase was washed repeatedly with warm water and dried in a rotary purifier. The transformation was confirmed by NMR measurement. Example 3G to 38: Synthesis of poly(fluorenyl) fluoroalkyl acrylate Repeat Example 29 to convert an alcohol to a polyfluoroalkyl acrylate or a poly(decyl) acrylate fluorocarbon under methacrylfee The ester is reported in Table 4 in Table 4 to prepare a polyfluoroalkyl telomer having the following general composition:

Rf-A_CXY-z (IV) Example No. Iodide Example No. Carboxylic Acid A Carboxylic Acid Value Example Number Alcohol b Alcohol OH Value 46.7 Example No. (Methyl) Acrylate 29 K1 c "R3~ 1 10 48.3 T9 ^ 1 ο 10 48.3 "20 ~^ 48.2 30 Me ———~ 1?^ ir- 2 11 54.3 Ύ\ — 52.4 31 3 4 12 13 1 Λ 42.6 25.6 C r\ "22~ 44.0 25.3 32 h33 6 7 15 1 f. 57.0 38.9 'lA 58.3 37.5 34 35 Me C7Ha- CH3 / 1 u M.7 "26 52.4 36 Pr "h^ --- 121132.doc -29- 200808835

8 Q 17 86.4 27 83.9 37 Me ch3 y 18 44.6 28 44.0 38 Et ^2^14 c2h4- H z=C〇〇H Shell example 19, 21-24 : Z=CH2OCOCR6=CH2 ; Example 20, 25-28 : Z = CON(R4)R5〇COCR6 = CH2 methyl-, Et=ethyl_, pr=n-propyl _ Example 39 · Preparation of dispersion for textile surface processing (formulation ^) by loading The following components were vigorously stirred in a four-necked flask of a stirrer, a reflux condenser, an inert gas supply, and an internal thermometer to prepare a dispersion; 37·5 g of fluoroalkyl acrylate (from Example 29) 3 1·〇g of acrylic acid Octacoyl ester (SAc) 5·0 g glycidyl acrylate (GMA) 4·5 g hydroxyethyl methacrylate (hema) 30·0 g dipropylene glycol 〇·4 g dodecyl mercaptan 6 · 〇g lauryl alcohol / 16 oxidized ethyl adduct (nonionic surfactant A) 4.5 g N, N-dimethyl lauryl ammonium acetate (cationic surfactant a) 200.0 g water The emulsion was heated to 60 ° C under a stream of nitrogen. Next, 〇2 g of initiator 2,2,-diox-di-isobutyronitrile (AIBN> 60. underarm polymerization time of 1 hr.) was obtained, and the obtained dispersion had an amount of solid H + of about 34%. Surface-processed textiles' acidified the dispersion and diluted to 30 g/1. The dispersion was applied to a fiber-based base on a HVF 59301 laboratory liner barrier press from Mathis AG (Switzerland) 121132.doc -30- 200808835 The material was then used in an LTE laboratory dryer from Mathis AG (Switzerland) at 160. (: drying and heat treatment for 3 seconds. Commercially available textiles 53 〇 3 〇 6 from nel GmbH, NeUgersdorf were used as PES/C. The 65/35 substrate was comparatively coated. The wet coating amount was about 66% for all of the examples listed. The washing/drying procedure was included at 6 〇. 5 times under the wash cycle. The corresponding fabric piece was made from ballast fabric To a kilogram of knee-washing load. The amount of detergent required is 7 g per wash cycle, c〇ral intensive". The fabric piece is not dried between wash cycles. After washing, it is dried in a washer dryer. Washing fabrics. Example 4〇Preparation of dispersions for textile surface processing (formulation for preparation) The dispersion was vigorously stirred in an autoclave equipped with a stirrer, a reflux condenser and an internal thermometer under inert gas atmosphere: 69.5 g of fluoroalkyl acrylate (from Example 29) 19.0 g of dodecyl acrylate Ester (la) 8.5 g vinyl chloride (VC) 2.5 g N-methoxymethyl propyl decylamine (NM AM) 3 · 5 g hydroxyethyl methacrylate 30.0 g dipropylene glycol 0 · 5 g dodecyl Thiol 7 · 0 g stearyl sulfhydryl / 11 oxidized ethyl adduct (nonionic surfactant B) 4 · 〇g · 烧 dimethyl dimethylated gas (13⁄4 ionic surfactant b) 2 0 0 · 0 g water After the emulsion is heated to 60 ° C, 〇·6 g initiator 2,2,-azo-di-2-methylmercaptopropane dihydrochloride is added. Polymerization time at 60 ° C After 6 hours. Reaction 121132.doc 31 200808835, excess ethyl chloride was removed. The resulting dispersion had a solids content of about 38%. For surface-processed textiles, the dispersion was acidified and diluted to 30 g/Ι. Coating of textile substrates as described in Example 3 9. Example 41 · Preparation of dispersions for textile surface processing (Formulation 3) Preparation for dispersion The following components were vigorously stirred under an inert gas atmosphere in an autoclave equipped with a stirrer, a reflux condenser and an internal thermometer: 60.5 g of fluoroalkyl acrylate (from Example 29) 12.5 g of 2-ethylhexyl acrylate (2-EHAC) 15.0 g of vinylidene gas (vdc) 3·5gN-methoxymethylpropenylamine 1. 羟g-mercapto hydroxyethyl acrylate 35·0 g dipropylene glycol 0.7 g dodecyl mercaptan 6·〇g stearin //11 oxidized ethyl adduct (nonionic surfactant b) 5.0 g sodium dodecyl sulfate (SDS) 200.0 g water after the emulsion is heated to 60 ° C, add 0.5 g initiator 2,2,_azo_di_2_methylmercaptopropane dihydrochloride. The polymerization time was 6 hours at 6 〇t. After the reaction, excess vinyl chloride was removed. The resulting dispersion had a solids content of about 36%. The dispersion was acidified and mixed with a C?sum HML (clariant) A20 wt% aqueous solution of magnesium chloride to give a liquid concentration of 30 g per liter in each case. Coating of the textile substrate was carried out as described in Example 39. 121132.doc -32- 200808835 Examples 42-45: The preparation, coating and testing of dispersions for textile surface processing are similar to Example 39. Examples 46-49: The preparation, coating and testing of dispersions for textile surface processing are similar to Example 40. Examples 50-53: The preparation, coating and testing of dispersions for textile surface processing were similar to Example 41. The isopropanol resistance (IpA), oil repellency (oil) and water repellency (water) of the dispersions from the spirits 39 to 53 are reported in Table 5. Example 54 · c8F17(CF2CF(CF3)a(CF2CF2)bCF2COOK synthesis friend added from the example ^76.2 g (G_55 m. 丨) poly I alkyl (4) to the dilute solution (1〇wt%) and in the order The lowering of the sandalwood 。 hours. The polyfluoroalkylcarboxylate potassium salt was dried by evaporation with azeotropic distillation with benzene. Examples 55-57 - Synthesis of polyfluoroalkyl sulphate per ton 54 Conversion of the polyfluoroalkylcarboxylic acid of the phenotype 11 to the corresponding polyfluoroalkyl carboxylate by reaction with sodium hydroxide, lithium hydroxide and ammonia. 121132.doc -33 - 200808835 5 Formulation 3 m P; tn dd 9 Ό ii 1 i '―' if^> ooiii iri 35.0 60 4-5 80-90 Ο 7 Ο ν〇m οο (NV〇m in d <N· to .q Ό ii — i — i ro — Oo 1 1 1 35.0 ο ο inch inch ο ο ο inch inch οο S cn ir> Ο (N i〇ν〇1 1 1—* 1 rH 1 ΓΠ * qoiv〇, i in 35.0 60 4-5 80-90 ί45 1 4 70-80 mm IT) d csi ^ 〇Ό i · — · — ΓΠ »~resistant qoi VO i 1 35.0 ο wn ο Ον Ό — ο ο α i〇 — Τ*·Η ON (N ιτ) vn O r4 ^ ^ V〇it ^ i < i ΓΠ i—iooi vd ii ^ 35.0 Ο Ο Ον ν〇τ -η 70 6 90-100 Formula 2 Os OO m S ^ ^ ^ v〇i ^ ! oo ii cs mopii inch · i 30,0 0^0 ΟΟ Ό τ—( ο ο 00 ... — m 69.5 19 8.5 2.5 3.5 Qoii inch·30.0 40 5 80-90 ^ ^ ο inch inch Smm S ON ^ ^ ^ Ό i — i oo ii (N m 〇oi ^ i 30.0 ο ο ο ΟΝ ν〇— 90 5 90-100 <N m 69.5 -1 19 8.5 2.5 3.5 oo • 丨 丨 1 1 30.0 1 80 5-6 90-100 ο ο 00 οο Ο Os <N 69.5 19 8.5 2.5 3.5 Ο ο t 1 I 30.0 ο ο ο Ct\ Γ ^* »—1 ο ο 00 ν〇—Formula 1 yr) 〇S ^ ΓΠ ΓΠ 鲁 iiii ο V〇ι ^ ι ι 30.0 ο ο ν〇〇〇νο Ο Τ Τ) οο 5 〇 · · “ 〇 ^ Mmiii ο 'Ο ^ ι . 30.0 90 5 ί 90-100 ι_ ο ο Ον ...Ον rn 37.5 31.0 5.0 4.5 Ο β ι 寸 · 1 1 1 30.0 1 tn ^ ο inch inch Ον 40 4 70-80 α 〇ro cn i 1 iii Ο νη .丨 inch丨 I 30.0 Ο m ο Ον Ό »-η ο $ § οο ι〇—ON m Os (N wo K a A. cn ΓΠ i 1 1 ο vd I Tt II 30.0 1 0^0 OO VD — 60 6 90-100 Polyfluoroacrylate No. Polyfluoroacrylate Quantity SAC LA 2-EHAC VC VDC GMA N-MAM HEMA < CQ < CQ ίϊ ® ® ^ 趄犁恕犁谀昶昶昶 v§ rr^L · rryL· rtyL· rtyL· IXK^s 〇ΚςΝ BK^s 4ttL 4ttL AM ▲ rrs mmmw γΐ Dipropylene glycol ΙΡΑ oil water ΙΡΑ oil wash before 5 washes 121132.doc -34-

Claims (1)

200808835 X. Patent application scope: 1. A fluorine-containing telomer compound of the formula IV: Rf-A-CXY-Z (IV) wherein RF is a group having a perfluoroalkyl group having 1 to 20 carbon atoms and having the following formula : CF2 —CF— L丨丄CFrCXv] i L __ ~ or b—CF2 CXY —CF5—CF— Ri — Jb , L, 1 J z is CH2〇R3 or COO· 1/q Mq+ or C〇 N(R4)R5OR3, X and Y are H, Cl or F, r1 is CF3, or2, Cl, Br or I, R is perfluorodecyl, perfluoropropyl or perfluoropropoxypropyl, R3 is Η or COCR6=CH2, R4 is an anthracene or an alkyl group having 1 to 6 carbon atoms, r5 is an alkylene group having 1 to 13 carbon atoms, R6 is H or ch3, Μ is a ruthenium or a metal cation or a cation Or substituted ammonium cation, q is the valence of hydrazine, a is 〇 to 10, and b is 1 to 30. 2. A compound according to claim 1 which is characterized by a heart. 3. A compound according to claim 1, characterized in that Ri is cF3. 4. A compound according to claim 1 which is characterized in that X and γ are ρ, or X is F and Y is C1, or X and Y are hydrogen. 121l32.doc 200808835 5 - A compound according to claim 1, characterized in that a is from 0 to 5. 6. The compound of claim 1 which is characterized in that the RF is a polyfluoroalkyl group having from 1 to 3 fluorinated carbon atoms. 7. The compound of claim 1 which is characterized in that the RF is a polyfluoroalkyl group having 4 to 16 fluorinated carbon atoms. 8. A compound according to claim 1 which is characterized in that the molecular weight of the compound of formula IV is greater than 750 g/mol. 9. The compound of claim 1 which is characterized by a+b>3. 10. A copolymer comprising a monomer of formula IV as claimed in claim 1 wherein Z is CH2OCOCR6=CH2 or CON(R4)R5OCOCR6=CH2, one or more non-fluorinated polymerizable vinyl monomers, Or a plurality of thermally crosslinkable or isocyanate-reactive monomers and optionally chlorine-containing polymerizable vinylic monomers. 11 a copolymer comprising the following contents based on the total weight of the copolymer: a) 20 wt% to 99. 5 wt% and preferably 40 wt% to 90 wt% of the formula IV of claim 1 Monomer, wherein Z is CH2OCOCR6=CH2 or CON(R4)R5OCOCR6=CH2, b) 0 wt% to 80 wt% and preferably 10 wt% to 50 wt% one or more of fluorine-free polymerizable ethylene Monomer and/or c) 0.5 wt% to 20 wt% and preferably 1 wt% to 10 wt% of one or more heat-crosslinkable or isocyanate-reactive monomers. 12. A copolymer comprising, by weight of the total weight of the copolymer: a) 40 wt% to 99 wt% and preferably 45 wt% to 85 wt% as claimed in claim 121132.doc 200808835 1 a monomer of formula IV, wherein Z is CH2OC〇CR6=CH2 or C〇N(R4)R5OC〇CR6=CH2, b) 0 wt% to 50 wt% and preferably 0.01 wt% to 30 wt% one or more a fluorine-free polymerizable vinyl monomer and/or c) from 0. 5 wt% to 20 wt% and preferably from 1 wt% to 10 wt% of one or more heat-crosslinkable or isocyanate-reactive monomers and d) 0. 5 wt% to 50 wt% and preferably 2 wt% to 30 wt% of the chlorine-containing polymerizable vinyl monomer. 13. Use of a copolymer according to any one of claims 10 to 12 for the water repellent, oil repellent and soil repellent surface treatment of fibrous substrates. 121132.doc 200808835 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: rf-a-cxy-z (IV) 121132.doc