TW200811200A - Fluorous telomeric compounds and polymers containing same - Google Patents

Abstract

Claimed are fluorous telomeric compounds of the formula RF-A-CH=CH(CH2)cCONR2(CH2)d-Z, where RF is a perfluoroalkyl radical of 1 to 20 carbon atoms, A is a group of the formulae, R1 is CF3, OR3, C1, Br or I, R2 is H or alkyl of 1 to 4 carbon atoms, R3 is perfluoromethyl, perfluoropropyl or perfluoropropyloxypropyl, X and Y are H, C1 or F, Z is -OH, -OCOCH=CH2 or -OCOCCH3=CH2 a is from 0 to 10, b is from 1 to 30 and c and d are independently of one another from 1 to 11. These compounds are copolymerized with further monomers. The copolymers thus obtained are useful for water-, oil- and soil-repellent finishing of fibrous substrates.

Description

200811200 IX. Description of the invention: [Technical field to which the invention pertains] The compound to be used is often used as a surfactant or wet _, 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 goods, non-wovens and paper, and hard substrates such as wood, concrete or concrete. The substrate thus treated is reduced in the inhalation of hydrophilic or hydrophobic liquids and promotes the removal of one of the existing ones. ^ ^

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 a tuned compound. Unexamined German Patent Application No. 10 2006 001 218.6 describes a murine telomer compound of the formula:

Rf-A-[CH2]cCR2R3-Z wherein KF is a perfluoroalkyl group having 1 main 2 carbon atoms, and A is a group of the following formula

——CF—CFL I · R1

^CF-CXY- CFj-CF - L b L ! J R1 r1 is CF3, OR4, Cl, Bi* or I, R2 and R3 are ruthenium, alkyl or aryl, I is perfluorodecyl, perfluoropropene Base or perfluoropropoxypropyl group, X and Y are H, C1 or F, Z is -OH, -0C0CH=CH2 or -〇C〇CCH3 = CH2, 121133.doc 200811200 a is 0 to 1〇,匕For 丨 to 3〇, and to 3〇. In order to be used as a surface modifying substance, perfluoron moths are usually first converted to perfluoroalkylethyl group together with ethylene. It is then said that the decylethyl ketone can be converted to the corresponding perfluoroalkyl alcohol by a suitable reagent. Next, the corresponding (meth) acrylate monomer of formula I can be prepared from total gas alkyl alcohol.

RfCH2CH2OCOCR=CH2 (1) It is well known that various derivatives of acrylic acid and methacrylic acid are prepared separately from the acrylic vinegar and methyl acrylate vinegar according to formula I and are well documented. The copolymers prepared therefrom are particularly useful for modifying the surface to render them oil-repellent, water-repellent and soil-repellent, for example, for surface processing textiles or for coating leather products and paper. Formula 1 is known for similar applications; [Fluoromonomer RFS〇2NRXCH2) n〇C〇CR=CH2 (II) The fluorinated fluorinated acid fluoride compound used for its synthesis is obtained via electrochemistry. It has been determined that for both monomer types (1 and „), the surface is coated with a longer and ideally linear perfluoroalkyl chain consisting of 8-1G fluorinated carbon atoms. A low molecular weight containing compound (including the monomers described above) having a linear all-gas base bond containing 8 fluorinated carbon atoms can be degraded to form perfluorooctyl sulphate and perfluorooctyl group, respectively. Sulfonic acid. It is believed that these degradation products will not be further resolved and therefore they are stable. Furthermore, it is believed that these compounds accumulate in vivo. Therefore, in recent years, various proposals have been made to prepare environmentally acceptable perfluoroanthracene. Compound 121133.doc 200811200 Compound. WO 02/16306 describes a branched fluorine-containing (meth) acrylate having the formula III,

Rf(Rf')CHOCOCR=CH2 (III) having a linear or branched perfluoroalkyl 'RF having 5 or less carbon atoms and a branched perfluoroalkane having 3 to 5 carbon atoms Base chain R〆. 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 W of living organisms. The WO 03/062521 patent describes a textile surface treatment based on a perfluorooctane sulfonic acid derivative in accordance with formula II: RFS02NRf(CH2)n〇COCR=CH2 (II) The perfluorobutyl group The sulfonic acid derivative has a partially branched perfluoroalkyl group Rf having 4 fluorinated carbon atoms, 2, and RLH, 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, and the degradation product of RfCH2CH2OCOCR=CH2 (I) may be more easily eliminated from the living organism. WO 02/34848 describes the use of trifluoromethyl or pentafluoroethyl as a perfluoroalkane-based polyglycidyl. Such compounds are also indicated for use as a gas-containing interface, an active agent or an environmentally acceptable perfluoroalkyl-containing compound 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 environmentally-friendly alternative to perfluoroalkyl compounds to date has been shown to be less effective than the use of such compounds as a basis for oil and water repellent surface processing. This is reflected in the achievement of 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 an alcohol, methacrylic acid, and/or acrylate functionalized fluorine-containing telomer compound having a molecular weight of preferably greater than 75 Å g/m Torr. The present invention further provides a fluorine-containing compound which is composed of a partially branched and partially linear polyfluoroalkyl chain which has a lower temperature than the melting of an equal molecular weight composed of a linear polyfluoroalkyl chain. Melt at temperature. The invention further provides a thin, mercapto acrylate or acrylate functionalized fluorotelomer compound prepared from the corresponding fluoroalkyl iodide. One aspect of the invention is the production of a copolymer of a telomeric compound of methacrylate or acrylate acrylate functionalized beta. • The invention further provides for the use of a specified compound or copolymer thereof for coating a surface of a substrate. The present invention further provides the copolymers described herein for imparting oil repellency and water repellency to fibrous substrates such as carpets, textiles, leather products, nonwovens and paper, and hard substrates such as wood, metal or concrete. Use in the manufacture of compositions of soil repellency 121133.doc -10 - 200811200. The present invention provides a fluorine-containing telomer compound of the formula IV:

RF-A.CH=CH(CH2)cCONR2(CH2)d.Z wherein RF is a perfluoroalkyl group having 1 to 20 carbon atoms, and A is a group of the formula:

-CF2 —CF' 1 1 ~ R1 a -

• CFrCXY- -CF-CF- - _ b LIJ Ri R is CF3, OR3, Cl, Br or I, reverse 2 is hydrazine or an alkyl group having 1 to 4 carbon atoms, R3 is perfluorodecyl, perfluoro Propyl or perfluoropropoxypropyl, X and Υ are H, C1 or F, Z is β〇Η, ococh=ch2 or -ococch3 = ch2, a is 0 to 10' b is 1 to 30, and c and d are independent of each other from 1 to 11.

Preferred are fluorine-containing compounds of the formula IV having a molecular weight of more than 750 g/m〇l. Especially preferred are compounds of the formula having a molecular weight greater than 1000 g/m〇l. The polyfluoroalkyl group may be a polyfluoroalkyl group having a single chain length or a polyfluoroalkyl group having a different chain length (CF3, C2F5, C3F7, c4F9, (6F13, c8Fi7, CiqF2i, C^F25, a group)) a mixture of polyfluoroalkyl groups which may or may not be branched. Preferably, the compound of the present invention having a saturated polyfluoroalkyl group Rf has a chain length of from 1 to 20 fluorinated carbon atoms and comprises at least one The end is preferably a fully vaporized carbon chain RF having (1) or 4 to 16 vaporized carbon atoms.

Ri is a large-volume group having a crystallization inhibiting effect on a polyfluoroalkyl chain. Particularly preferred are all-based, perfluoro-etherether groups or chlorine atoms, bromine atoms or iodine atoms. The perfluoromethyl group is the best. R2 may be hydrazine or an alkyl chain having 1 to 4 carbon atoms. I is preferably hydrogen or methyl or ethyl.尺3车乂 ‘is perfluoromethyl|, perfluoropropyl or perfluoropropoxypropyl. The perfluoromethyl group is the best. a preferably 〇 to 1 〇 b is preferably 1 to 3 〇 c, preferably 1 to 11 d, preferably 1 to η and more preferably 0 to 5. And better a+b>3. More preferably, c = 1, 2, 7, or 8. And more preferably d=2 or 3. X and Y can be independently H, C1 or F. X and Y are preferably gas atoms. Alternatively, X is a fluorine atom and Y is a gas atom, or X and Y are a hydrogen atom. Fluorinated amide alcohols of cadaver IV (Z = 〇H) are typically obtained from the corresponding polyfluoroalkyl iodides in a multistage process. In the first step of the process (referred to as telomerization), a fluorine-containing compound (polymerization inhibitor) capable of transferring a radical chain and at least one fluorinated monomer are transferred via a radical formation mechanism at 20-25 (TC). (backbone) reacts to form a telomer of the formula:

Rp, AI incorporation of a modulating agent comprising a fluorine-containing alkyl compound having a radically separated group, such as a fluorine-containing alkyl iodide, a fluorine-containing alkyl bromide, a fluorine-containing alkyl mercaptan, containing 121133.doc - 12- 200811200 Fluoroalkyl sulfide and fluoroalkyl alcohol. Preferred is a mixture of perfluoroalkyl iodides having a single chain length or perfluoroalkyl iodides having different chain lengths. Perfluoroalkyl group may be branched or unbranched 'for example, all gas sulfhydryl iron, perfluoroethyl group, normal perfluoropropyl iodine, isoperfluoropropyl iodine, n-perfluorobutyl iodine, isoperfluorobutane Isomers of quinone iodide, third perfluorobutyl iodide and perfluorohexyl iodide, perfluorooctyl iodide, perfluorodecyl iodide and perfluorododecyl iodide. Preferred are perfluoroalkyl iodides of the invention having a chain length of from 1 to 20 carbon atoms and at least one terminal CF3 group. Particularly preferred is a perfluoromethyl group having 6 to 16 fluorinated carbon atoms or a chain length of 8 to 16 fluorinated carbon atoms and an average chain length of about 7.5 fluorinated carbon atoms or about 9 fluorinated carbon atoms. Technical grade mixture of iodine, perfluoroethyl iodide, perfluoropropyl iodide or perfluoroisopropyl iodide or various perfluoroalkyl iodides. The addition of the backbone to the telomer results in the gradual formation of higher molecular weights. The telomer thus formed consists of a perfluoroalkyl chain having a terminal iodine group. The manner in which the main chain is incorporated into the telomer is different depending on which of the following three variants is selected. In the first variant, only the fluorinated unsaturated monomer CFfCFR! was initially added to the telomer. The product is then added to the monomer of formula CF2 = CXY under telomerization conditions. The telomer thus obtained has the formula

Rf - -CF? -CF- a CF^CXY- L 1 - R1 a L " and shows the incorporation of monomers by block. In the second variant, only the fluorinated unsaturated monomer was initially added 12I133.doc •13- 200811200 Addition CFfCFR^ CFfCXY. The monomer of the product is then conditioned under conditioned conditions. The obtained telomer CFr-CF-rf——CFj-CXY-

Ri also shows that the monomers are incorporated block by block, but the monomers are added in reverse order. In a third variant, the simultaneous addition of a mixture of the two monomers results in a random incorporation of monomer CF2 = CFRa CF2 = CXY. An example of a compound of the formula cf2=cfr丨 is m ethylene, desert triethylene ethylene, moth trifluoroacetamidine, a full-form methyl vinyl bond, a full-dose ethyl vinyl ether, a full-gas propyl vinyl scale, a full-propyl propyl vinyl And branched and unbranched perfluoroolefins having terminal double bonds, such as hexafluoropropylene, perfluorobutene, 1-perfluorohexyl or perfluorooctene. Examples of the cut 2 = CXY chemical are, for example, ethylene, vinylidene gas, chlorotrifluoroethylene, trifluoroethylene, i-dichloro-2, 2-diethylene and h-chlorodifluoroethylene. In the case of an iodine-containing compound, the radical which initiates the telomerization reaction can be produced by a source capable of forming a radical. Suitable sources for the formation of free radicals include light or heat. The light source typically has a maximum in the infrared to ultraviolet region. The formation of free radicals attributed to heat usually occurs between ah and gift. Suitable sources for the formation of free radicals include chemical radical initiators which also reduce the reaction temperature required for free radical formation to zero. . Between W and C, such as organic or inorganic peroxides, azo compounds, and 121133.doc -14-200811200 machines and inorganic metal compounds and metals and combinations thereof. In particular, acid salts, fluorinated and unemulsified organic peroxides, azo compounds and metals of = Ru, Cu, Ni ' Pd and Pt. The telomerization reaction can be carried out in the absence of a solvent, in a solution, in a suspension or in an emulsion. Solvent-free or reaction in an emulsion is especially preferred. The telomer is first converted to an aqueous emulsion with the aid of a surfactant, in the event that the emulsion conditions the reaction. The emulsion can be stabilized by anionic, cationic, nonionic or amphoteric surfactants and combinations thereof. For example, fluorosurfactants are particularly suitable (the reaction usually takes place at elevated temperatures via the addition of a backbone and a free radical initiator. Additional components can increase the yield of the reaction, such as small amounts of sulfite, bisulfite or even An aqueous solution of a sulfate. The polyfluoroalkyl carbon obtained by the telomerization reaction is then converted to the corresponding polyfluoroalkylguanamine. To achieve this, the indoleamine CH2-CH(CH2)cCONR2(CH2)d of formula VI -OH (VI) is prepared first from a terminally unsaturated linear monocarboxylic acid or a corresponding ester derivative and an amine alcohol HNR2.(CH2)d^〇H (V) of the formula v. Usually in the absence of a solvent The reaction is carried out by heating the mixture at a temperature between 4 ° C and 180 ° C for a period of 1 to 5 hours. Examples of terminally unsaturated linear monocarboxylic acids are acrylic acid, 3-butenoic acid, 4-anthracene. Oleic acid, hexamic acid, 6-heptamic acid, 7-octenoic acid, decenoic acid, 9-anthracene acid and undecylenic acid. Particularly preferred examples are 3-butenoic acid, 4-pentenoic acid 9-decenoic acid and 121133.doc -15- 200811200 ίο- undecylenic acid Examples of the first amino alcohol are 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 2 - Amino-1-butanol, % amidopentanol, 2-aminopentanol, 6-aminohexanol. Examples of the second amino alcohol are 2-methylaminoethanol, hydrazine methylaminopropyl Alcohol, 4-mercaptoaminobutanol, 2-hydrazinoamine "-butanol, methylaminopentanol, 2-decylamino-1-pentanol, 6-methylaminohexanol , 2-ethylaminoethanol, 3-ethylaminopropanol, 4-butylaminobutanol, 2-ethylamino group

1-butanol, 5-ethylaminopentanol, 2-ethylamine + pentanol, 6-ethylaminohexanol, 2-propylaminoethanol, propylaminopropanol, private Aminobutanol, 2-propylamino-1-butanol, 5-propylaminopentanol, 2-propylamino-pentanol, 6-propylaminohexanol, 2, butyl Aminoethanol, 3-butylaminopropanol, 4-butylaminobutanol, 2-butylaminobutanol, butylaminononanol, 2-butylamino-1-pentanol, and 6 _butylaminohexanol. Particularly preferred are 2-aminoethanol, 3-aminopropanol, 2-methylaminoethanol, 2-ethylaminoethanol and 3-propylaminoethanol. The guanamine alcohol VI is then reacted with a polyfluoroalkyl moth in a free radical reaction, and the intermediate formed is subsequently dehydrohalogenated to form a polyalkylene ketamine of formula VII. RF-A-CH=CH(CH2)cC〇NR2(CH2)d-〇H (VII) The polyfluoroalkyl hydrazine becomes a dilute hydrocarbon VI via a free radical process which can be carried out similarly to the telomerization reaction described above. The reaction proceeds. The reaction can be carried out in a solvent or without a solvent. Examples of the solvent are ketones such as acetone, methyl ethyl ketone, methyl propyl ketone or dimethyl ketone | χ 土 叫 A A 丞 丞 丞 丞 , , , , , , , , , , , , , , Vinegar; alcohol, such as corn, 7^^ sub-province θ θ, B%, butanol; ether, such as dioxins 121133.doc -16-200811200 or tetrahydrofuran, hydrocarbons such as toluene or octane; For example, diterpenoid guanamine and inner moon females, such as N-mercaptopurine, are more than 13 ketones. Subsequently, the thus obtained iodine-containing perfluoroalkylguanamine can be converted into an unsaturated polyfluoroalcohol by reacting with a base. This reaction is usually carried out in water at a temperature of from 50 〇c to 1 Torr (rc in the presence of a base for several hours. Examples of such bases are sodium hydroxide, potassium hydroxide, sodium methoxide or 1> 8-diazabicyclo ( 5.40)·11-dilute (DBU). After the reaction, the product can be separated and washed by phase separation, or the solvent can be recovered by distillation. The main product formed is mainly trans-dilute hydrocarbon. The polyfluoroalkylguanamine obtained in this manner can be reacted with (meth) acrylate, acid or decyl chloride to form the corresponding gas (mercapto) acrylate of the formula (1) and hydrazine. RF-A- CH=CH(CH2)cCONR2(CH2)d〇C〇CH-CH2 (VIII) and RF-A-CH=CH(CH2)cC0NR2(CH2)d0C0CCH3 = CH2 (IX) and (meth)acrylate fluorenyl The gas reaction is usually carried out in the presence of a base such as triethylamine to combine the formed vaporized hydrogen. A suitable catalyst (for example, a tin catalyst) can be used for transesterification. The compound of the formula VIII or IX can be polymerized with fluorine-free. Copolymerization of a vinyl monomer and/or a chlorine-containing polymerizable vinyl monomer and optionally one or more thermally crosslinkable or isocyanate reactive monomers. For copolymers containing the following: based on the total weight of the copolymer: a) 20 wt% to 97 wt% and preferably 40 wt% to 90 wt% of the formula IV 121133.doc • 17- 200811200 Wherein Z is -0 (:0 €11 = (: 112 or -0 (:0 (:: 113 = (:112, b) 0 wt% to 80 wt% and preferably 10 wt% to 50 wt% One or more fluorine-free polymerizable vinyl monomers 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 The invention further provides copolymers (based on the total weight of the copolymer) comprising: a) 40 wt% to 90 wt% and preferably 45 wt% to 85 wt% of a monomer of formula IV, wherein Z is An ococh=ch2 or -〇cocch3 = ch2, b) 0 wt% to 50 wt% and preferably 0.01 wt% to 30 wt% of one or more fluorine-free polymerizable vinyl monomers and/or c) 0.5 From wt% to 20 wt% and preferably from 1 wt% to 10 wt% of one or more of the thermally crosslinkable or isocyanate-reactive monomers and d) from 0.5 wt% to 50 wt% and preferably 2 wt. Up to 30% by weight of a chlorine-containing polymerizable vinyl monomer. The optional comonomer (b) is fluorine-free (no fluorine) and is represented by a variety of commercially available acrylates and mercapto acrylates and styrene derivatives. Examples of non-fluorinated comonomers are hydrocarbyl esters and decylamines of unsaturated carboxylic acids. These include, for example, acrylic acid, mercaptopropionic acid, alpha-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid and the following esters of itaconic acid and guanamine: vinyl, allylic Base, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 3,3-dimercaptobutyl, heptyl, octyl, isooctyl, Twelve alkyl, hexadecyl, stearyl, 222, cyclohexyl, decyl, isobornyl, phenyl, phenyl fluorenyl, adamantane 121133.doc -18- 200811200 base, toluene Base, (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 hexanoate and vinyl heptanoate; alkyl vinyl ethers and alkyl olefins An ether such as hexadecyl vinyl ether, lauryl vinyl ether, octadecyl vinyl ether and ethyl vinyl ether; a non-saturated nitrile such as acrylonitrile or methacrylonitrile, Α-chloroacrylonitrile, α-cyanoethyl acrylate; aminoalkyl (meth)acrylate, such as ruthenium (meth)acrylate, ruthenium-diethylaminoethyl ester, small (meth)acrylic acid Third butylaminoethyl ester; alkyl (meth) acrylate having an ammonium group, such as fluorenyl methacryloxyethyl decyl ammonium chloride; styrene and its derivatives, such as vinyl toluene , α-methylstyrene, α-cyanomercaptostyrene, chlorodecyl styrene, olefins such as ethylene, propylene, isobutylene, butadiene, isoprene and oxime (曱基). Particularly preferred optional comonomers may be the following esters or decylamines of acrylic acid and methacrylic acid: methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, ten as described above Tetraalkyl, dodecyl, octadecyl, methoxy poly(ethylene glycol) and methoxy 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 hydroxyl group, an amine group, an N-alkyl alcohol oxime group, an isocyanate group or a protected isocyanate group. Examples of comonomers having one or more crosslinkable groups include unsaturated carboxylic acids and acrylic acid, methacrylic acid, alpha-chloroacrylic acid, 121133.doc -19-200811200 bar smear, maleic acid, An acid anhydride of fumaric acid and itaconic acid, including a monomer of a turmeric group, such as hydroxyethyl (meth) acrylate and hydroxypropionin (meth) acrylate, butyl methacrylate , poly(ethylene glycol) mono (carboacetic acid vinegar, poly(propylene glycol) mono (meth) acrylate, poly (ethylene glycol) winter poly (propylene glycol) mono (methyl) acrylate, poly Tetrahydrocyanate mono(methyl)acrylic acid, N ^methyl (meth) acrylamide, butyl vinyl _. Other crosslinkable precursors such as (meth) acrylic acid Vinyl, vinegar, (meth) (tetra) acid acryl

S曰, methoxymethyl acrylamide, N_isopropoxy methacrylamide, N-butyl methacrylate, N•isobutoxymethyl propylene amine, (A) Base) Acrylic glycidol and isocyanate α,α-dimethyl-m-isopropylbenzophenone. Other examples are the release of isocyanate-branched monomers under high temperature or light irradiation, such as ageing, ketone and wow-protected isocyanate-terminated (alkyl methacrylate. Earth; ~ Zhaoxing The dry body (d) contains a 丨·丨 muscle~ only (eight) sentence nationalization, olefins such as vinyl chloride, vinylidene chloride, 3 gas small isobutylene, chloroprene, dichlorobutadiene and 2 , 5-dimethyl dimethyl diene. Vinylene vinyl chloride and vinyl chloride are particularly preferred alternative comonomers. The comonomers described in the literature are usually prepared by free radical polymerization techniques, such as straw. It is especially preferred to prepare a polymeric variant by solvent, emulsion, microemulsion or miniemulsion polymerization techniques. The emulsion polymerization of the monomers takes place in the presence of water, interfacial activity and optional organic solvents. By means of a high pressure homogenizer or the like 'The mixture can be pre-emulsified in the polymerization enthalpy. The polymerization is carried out in the presence of a free radical initiator at a temperature between 5 CTC and 150. (Alternative or combined use of various anions, cations, nonions or Both sexes 121133.doc •20- 200811200 > sub-interface live students Examples of nonionic surfactants include poly(ethylene eicosyl-, K-ethylene glycol) tridecyl squama, poly(ethylene glycol) cetyl _, poly(ethylene glycol) - Poly(propylene glycol) hexadecyl ether, poly(ethylene glycol) stearyl alcohol, poly(ethylene glycol) oleyl _, poly(ethylene glycol) bismuth ruthenate, poly(ethylene glycol) octane Base, poly(ethylene glycol) monododecanoate, poly(ethylene glycol) fatty acid ester, poly(ethylene glycol) monooleate, sorbitan monodecanoate, dehydrated sorbus Sugar alcohol monostearate, sorbitan single brown φ 彳] 1 g 曰 sorbitan monostearate, sorbitan monooleate, saponin, sorbitan sesquiole oleic acid, dehydration Sorbitol trioleate, poly(ethylene glycol) sorbitan monododecate, poly(ethylene glycol) sorbitan monopalmitate, poly(ethylene glycol) sorbitan Barium stearate poly(ethylene glycol) sorbitan monooleate, poly(ethylene glycol)_co-poly(propanol) polyglycerol fatty acid ester, poly-modified Shishi oil and all Fluorine burnt soil The amount of the nonionic surfactant used is in the range of 01% to 1% by weight relative to the weight of the polymer. • Examples of the cationic surfactant of the present invention are based on saturated and unsaturated fatty acid amines. Ammonium compounds, such as octaammonium acetate, dodecyltrimethylammonium chloride, amine-functionalized polyethoxylates and polypropoxides, and interpolymer ammonium compounds, such as polyoxyethylene Dodecyl monodecyl chloro-ruthenium, an ammonium compound based on an arylamine, such as biphenyltrimethylammonium chloride, a saponin derivative, such as an ammonium salt formed from an animal lipid and an imidazoline a polyoxo-based cationic surfactant and a fluorine-based cationic surfactant. The amount of cationic surfactant used is in the range of 0.1 wt% to 1 wt%, relative to the weight of the polymer. 121133.doc 200811200 Examples of anionic surfactants of the invention include fatty alcohol sulfates such as sodium lauryl sulfate and poly(ethylene glycol) lauryl ether sulfate; alkyl sulfonates such as twelve Sodium sulfonate; alkyl benzene sulfonate, such as nonylphenol ether sulfate, sulfosuccinate, such as sodium hexaether sulfosuccinate; fatty alcohol phosphates, such as sodium lauryl phosphate; And fatty acid salts, such as sodium stearate. The amount of the anionic surfactant used is in the range of 〇1 _% to 10 () wt 〇 / 相对 relative to the 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. In particular, it is an azo compound such as azobisisobutyronitrile (AIBN), azobis:: azobis(2-cyanodecanoic acid), 2,2, azobis(2-carbazide). Acetate) a two-sleeping acid salt, a hydrazine peroxide, such as cumene hydroperoxide, a gas peroxy group and a third pentyl hydroperoxide, a di---^^70 group (such as a peroxide Dibutyl and dicumyl peroxide), peroxidation series (such as benzoic acid and di-tert-butyl peroxyphthalate), A - benzammonium peroxide and peroxidized ten 1 b - Base (such as sulfuric acid and persulfate, such as a combination of a compound and a metal. A ° with an organic or inorganic gold chain transfer agent can be used in polymerization, such as alkanethiol. In solvent and emulsion polymerization, A Base ethyl ketone and methyl: butyl:: a ketone, such as propanol and butanol, xi-π such as ethanol, isopropanol, butyl ketone, such as butyl ketone , propylene glycol, dipropylene glycol, _ stone ^, 6-hexanediol, ethylene glycol and vinegar 'such as dipropylene glycol monomethyl 2:: and multiple (4) known early methyl ether, triethylene glycol 121133.doc -22- 2008 11200 Diterpenoid scale and diethylene glycol monobutyl ether acetate · Text, §, such as ethyl acetate, propyl acetate, butyl acetate, hexanyl-butyrate-s-butyl butyl ester and dibutyl Dibutyl acrylate; and halogenated hydrocarbons such as toluene, dimethyl hydrazine, octane, perchloroethylene and 丨3_dichloro-2,2,3,3,3-pentafluoropropane. The preferred solids content of the polymer dispersion is between 2% and wt%. 含 The I-containing copolymer containing the fluorine-containing monomer of the formula (IV) is suitable for coating fibrous substrates (such as carpets, textiles, leather products). , non-woven or paper) or hard substrates (such as wood, metal or concrete). These copolymers impart water, oil and soil repellency properties to such substrates.

Accordingly, the present invention also provides a method of treating a fibrous substrate with an aqueous fluorinated aqueous dispersion of the active hydrazine using the right BB. The content of the formulation of the present invention for surface-improving textiles and other sheet-like structures is selected to transfer sufficient repellent properties to the substrate being treated. The amount of wet coating was determined by weighing the surface-treated samples before and after coating. The fluorine-containing textile surface treating agent of the present invention can be used together with other additives, including water-repellent substances (such as (four), poly-dosage, hydrazine compound or stearate) and other oil-repellent substances, surfactants, insecticides, Flame retardants, antistatic additives, plasticizers, fixing agents and anti-wrinkle additives, the amount of which is such that the amount of stability fixed to the textile and the composition is not impaired by adding a reactive additive (such as The melamine resin, the protected isocyanate or the epoxide) crosslinks the fluorine-containing textile surface treating agent of the present invention. 121133.doc -23- 200811200 The fibrous substrate coated with the fluoropolymerizable dispersion may be, for example, carpet, spun, leather, non-woven, and paper. These are especially natural fibers (such as cotton, linen and silk), synthetic fibers (such as polyamide, polyester, polyamidoguanidine, polyolefin, poly(meth)acrylate, poly(vinyl chloride). , (enol)) semi-synthetic fibers (such as human cotton or acetic acid vinegar), inorganic fibers (such as broken glass fibers or ceramic fibers) or any combination of such specified fibers or such materials The composition of any desired combination of woven products. For coating, the substrate is typically immersed in a dilute dispersion of copolymer and optional additives. Alternatively, the dilute dispersion can be sprayed onto the substrate. The impregnated substrate is then extruded by a reel system to remove excess dispersion, dried in an oven and crosslinked at a temperature sufficient to ensure cross-linking on the substrate being treated to ensure that the substrate is treated. The time of cross-linking on the material. This crosslinking method is usually carried out at a temperature between 50 C and about 19 (TC, in general, at a temperature of about to war and especially from about 2 seconds to as long as H to the temperature of the shoe). Suitably, it is preferably from 5 seconds to $ minutes. Another alternative method of applying the formulation to the substrate is foam coating, where the formulation in the crucible is applied to the substrate in a foamed form, followed by drying and applying to the m-bed coating, the formulation is typically 盥 additional as % w A thick foam of λ, , /, and an external foaming agent is added. High consistency formulations for foam coating are typically polymers. "There is a quantity of the same surface for the surface force of the textile τ < recording surface processing, can detect the water repellency of these textiles after the specific test, in the wash and then ^ isopropyl alcohol and oil repellency . According to the AATCC standard test, half of the 9 V丄, Jiang Y tends to be issued, and the method 22 measures the water repellency by the spray test. The U distillation nozzle was sprinkled onto the spun σ substrate to be tested, and then the wet type was visually compared to produce a value by referring to the picture evaluated in the method of test 121133.doc *24- 200811200. After spraying with water, the value of π m ν is related to the appearance of the surface and has the following meanings (Table 1): Table 1

,: The second test of the series water-isopropyl alcohol test solution can be used to reduce the isopropanity (IPA) of the soil material. The reported level of ιρΑ is the highest number of cores, where the fabric does not wet for 1 () seconds and the droplets still have a spherical or hemispherical shape. The wet substrate or the substrate that only rejects 1% water (〇% isopropanol) (ie, the minimum wet test solution) has a grade of G, and the substrate grade of 10% isopropyl alcohol_water is 10 . Intermediate levels can also be specified. According to the AATCC Standard Test Method 118, the oil repellency test substrate is capable of repelling oily dyeing'. A higher level within the evaluation range indicates a better rejection of the contamination, especially the oily liquid. In the test, standardized test drops (manufactured from a series of hydrocarbons with different surface tensions selected) were applied to the surface of the sample to be tested by careful pipetting, and visually after the specified contact time. Assess moisture. The oil repellency value corresponds to the highest number of test liquids which did not cause surface wetting. The standard test liquid has the following New Zealand (Table 2) ·· 121133.doc -25- 200811200 Table 2 Oil repellency composition level 1 Nujol® Grade 2 65 vol% of Nujol/35 vol% of the positive 16 burning grade 3 Burning grade 4 / n-tetradecane grade 5 n-dodecane grade 6 positive calcining grade 7 n-octane grade 8 n-g-burning Note: Nujol is a mineral oil from Plough Inc., which has 360/ at 38 °C. 3 90 Saybolt viscosity and a specific gravity of 0.880/0.900 at 15 °C. Prior art FC polymers currently give a 6 oil repellency value; grade 5 is often considered to be excellent. [Examples] Examples While the following examples illustrate the subject matter and advantages of the present invention, the materials and amounts recited in the examples are not to be considered as limiting. Synthesis Example 1 Synthesis of CH2 = CH(CH2)2CONHCH2CH2-OH 20.0 g (0.2 mol) of 4-pentenoic acid (Aldrich) was fed into a 250 ml four-necked flask. The acid was warmed to 50 ° C and gradually mixed with 18.3 g (0.3 mol) of ethanolamine. The reaction mixture was slowly heated to 180 °C. The formed water was removed by a Dean-Stark apparatus. The reaction mixture was stirred at this temperature for an additional 4 hours to carry out a supplementary reaction. Use GC monitoring 121133.doc -26- 200811200 The completion of the reaction. After the reaction, the volatile component was removed from the reaction mixture to obtain a liquid product. !H NMR (solvent: CDCIs): 2.0-2·3 (4Η, -(Cii2)2CO-), 3.4(2H, -NHCiLCHy), 3·6(2Η,,5.1-5·3(2Η, Example 2 : Synthesis of CH2=CH(CH2)8C0NHCH2CH2-0H 74.0 g (0.4 mol) of 10-H-enoic acid (Aldrich) was fed into a 250 ml four-necked flask at 40 ° C. It was added over 15 minutes with stirring. 25 7 g (〇42 m〇i) ethanolamine. During this process the temperature rose to 7 (TC. The reaction mixture was slowly heated to 180 C. It was formed by removal of the Dean_Stark apparatus. Water. The reaction mixture was stirred at this temperature for another 4 hours to carry out a supplementary reaction. The completion of the reaction was monitored using a GC. The reaction mixture was cooled to 50 ° C and mixed with 50 ml of ethanol previously heated to 50 ° C. Dissolved. The liquid was precipitated in water. Washing and drying left 73. 7 g of a white precipitate. iH NMR (solvent: CDCl3): 12-23 (16H, -(ca2)8C〇), 3.4 (2Η?^ΝΗΟΗ,ΟΗ,. 3.6(2H? -CH.CH.O-) . 4.9-5.1 (2^ strongly =), 5·8 (1Η, synthesis of CHfCD 〇 example Preparation of 110 g by vigorous stirring at 6 〇t: 018 m〇1)Flu〇wet I812*(Clanant), 15 g Flu〇r〇link c(s〇lvay s〇iexis , & An emulsion of ammonia M90 g water, and introduced it into the autoclave together with 2.5 g ammonium persulfate as the starting feed. After the pressure test, the purification was repeated with nitrogen. During the heating to 'C stage During the period, six rats of propylene and four m 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 121133.doc -27·200811200 bar until 82.5 g was added ( 0.55 mol) six-deficient women and 9 〇g (〇90 mol) of tetrafluoroethylene. After the pressure is lowered, the autoclave is cooled to room temperature, and the fluorochemical phase is separated by washing with salt and washed. Distillation separation of low molecular weight components. U.2% iodine content indicates an average molecular 〇19F NMR of about 14 〇〇§/111〇1 (solvent: CDci3/C6F6, compared to CFCl3): _59 8 (2F ' -Chi ) ' -71.8 to -77.0 (3F in each case, _CF_C£3), Han

-81.9(3F ′ -CF2_C£3) ’ _11〇.2 to _126 9 (2ρ j • C£2- in each case), -184.6 to -185.5 (1F, _C£(Cf3 in each case).

, ]Q F NMR spectrum is apparent that about 2 molecules of hexapropylene propylene have been incorporated into each perfluoroalkyl iodine used. The compound represented by 18 12 is a perfluoroalkyl fluorene having 6 to 14 fluorinated carbon atoms, each molecule having an average bond length of about 9 vaporized carbon atoms.

Flu〇r〇linkC is a perfluoropolyether carboxylic acid. Examples 4 to 12: Synthesis of polyunsole alkyl iodide Example 3 was repeated to prepare the corresponding polyfluoroalkyl moth (Examples 4 to 12). The results of the synthesis are shown in Table 3. Table 3 telomerization reaction to prepare and female, -, polyfluoroalkyl iodide having the general composition of the underarm: 12U33.doc -28- 200811200 Instance number ED Rf Rf [mol] a [mol] b [mol] c [ Mol] d [mol] Mn *[kg/mol] 4 (cf3)2cf- 0.25 0.55 2.23 - - 1.3 5 CgFn- 0.25 0.71 - 3.06 - 1.5 6 C2F5- 0.20 0.43 4.04 - - 2.4 7 QF17- 0.35 0.68 - - L75 1.2 8 1812-** 0.30 - 2.49 - 1.23 . 1.7 9 c8f17- 0.25 - - L98 1.01 1.3 10 (cf3)2cf- 0.18 0.20 雠1.83 - 0.9 11 1612-** 0.22 0.87 L32 - - 1.5 12 CeFn- 0.26 - - - 2.07 1.8 Determination of self-iodine content * * The compound expressed as Fluowet 16 12 and Fluowet 18 12 is a perfluoroalkyl iodide mixture from Clariant, each having 6 to 14 fluorinated carbon atoms, each having an average of A chain length of about 7.5 fluorinated carbon atoms and 9 fluorinated carbon atoms. Example 13:

Synthesis of C8F17(CF2CF(CF3))a(CF2CF2)bCH=CH(CH2)2CONHCH2CH2OH 5.0 g (0.07 mol) of the valine alcohol from Example 1 and 50 g of the polyfluoroalkyl iodide from Example 3 were fed into 200 ml In a four-necked flask. After the reaction mixture was warmed to 75 ° C, 0.1 g of AIBN was added. After 5 hours, the reaction mixture was cooled to 50 ° C and gradually mixed with 5 g of 50% sodium hydroxide. The mixture was then stirred at 75 ° C for an additional 3 hours, mixed with 20 g of toluene, and washed repeatedly with warm water. The product was obtained by removing the solvent by distillation. 4 NMR (solvent: CDC13/C6F6): 2.0 to 2.3 (4H, -(CE2)2CO-), 3·4 (2Η,.NHCH2CH2-), 3·6 (2Η, -CH2CE2〇-), 5.8 (1H , -CH=CliCH2), 6.3 (1Η, RFCE=CHl·). Examples 14 to 22: Synthesis of Polyfluoroalkylguanidamine 121133.doc -29- 200811200 Example 13 was repeated to prepare the corresponding polyfluoroalkylguanamine (see Examples 14 to 22). The results of the synthesis are reported in Table 4. Table 4 RF-A-CH-CH(CH2)cCONR2(CH2)d-〇H (VIII)

The reaction is carried out to prepare a gas-gas alkyl guanamine having the following general composition:

Example 23: Synthesis of C8F17(CF2CF(CF3))a(CF2CF2)bCH=CH(CH2)2CONHCH2CH20 COCH=CH2

9S.0 g (〇.〇6 m〇1) from the alcohol of Example 13, 〇8 acrylic acid, 〇·3 g fluorery acid and 0.4 g of p-methoxybenzene were fed into a three-necked flask. And this. Shell material force... to 80 C. During the reaction period, within 24 hours of the reaction, the pressure at the reaction temperature and 200 m b a r πτ 八^r* — • the water from the reaction. The organic phase was washed repeatedly with warm water and dried in a rotary evaporator. ^ NMR (solvent: CDCi3/C6F6): 2 g to 2 Cong, even from 〇_)^ 3.4(2H, -NHCH2-), 3.6(2H, -C^CH^O-), 5.8^6.5 (5Η, -Cii=C|i- and .Examples 24 to 32: Synthesis of poly(methyl)acrylic acid fluoroalkyl vinegar Repeat Example 23 with 佶咿 & Α β ★ polyalkylene feamine alcohol converted to polyacrylic acid Fluoroalkyl 121133.doc -30- 200811200 Cool (AC) or converted to poly(methyl)acrylic acid fluoroalkyl vinegar (MA) under methacrylic acid. The composition is reported in Table 5. Table 5 Preparation of poly(meth)acrylic acid fluoroalkyl ester having the following general composition:

Rf A CH CH(CH2)eC〇NR2(CH2)dQCQCH=CH2 (VIII) or RF-A.CH=CH(CH2)cC〇NR2(CH2)dOCOCCH3=CH2 (ΐχ)

37·5 g polyacrylic acid fluoroalkyl group g (from the example υ) 3 1 · 0 g octadecyl acrylate (SAc) 5 · 0 g methacrylic acid glycidol _ (GMa) 4 · 5 g thiol Hydroxyethyl acrylate (Hema) 30·0 g dipropylene glycol 0.4 g dodecyl mercaptan 6·〇g dodecyl alcohol/16 oxidized ethyl adduct (nonionic interfacial activity 121133.doc -31 - 200811200 Agent A) 4·5 gN,N-didecyldodecyl ammonium acetate (cationic surfactant A) 200-0 g water The emulsion is heated to 6 (TC) under a strange nitrogen flow. Then add 〇2 g The initiator 2,2,-azo-di-isobutyronitrile (AIBN). The polymerization time at 6 〇t is 1 〇h. # The resulting dispersion has a solid content of about 34%. It is a surface-processed textile product. The dispersion was acidified and diluted to 30 g/ι. The dispersion was applied to a fiber substrate from # HVF 593〇i laboratory liner_roller from # MathiS AG (Switzerland), followed by from Mathis AG (Switzer) 〗 〖and^ LTE laboratory dryer at 16 (dry and heat treatment for 3 sec. rc. Commercially available textiles from nel GmbH, NeUgersdorf Sahara 53〇3〇6 for PES/Co 65/35 substrates for comparative coating Right The wet coating amount is about 66% for all of the examples. The washing/drying procedure includes 5 wash cycles at 6 ° C > c. The corresponding fabric sheet consists of a ballast fabric to a kilogram of wash load. The amount of detergent is 7 g "Coral intensive" per wash cycle. #H strips are not dried between fabrics. Washing, drying the fabric in a laundry dryer.: Example 34 · For textiles Preparation of surface-treated dispersion (formulation hook; for preparing the dispersion, the following components are vigorously stirred in an inert gas atmosphere in a south autoclave equipped with a stirrer, a reflux condenser and an internal temperature juice. 69·5 gl Dilute fluoroalkyl ester (from example u) do g lauryl acrylate (LA) 8·5 g vinyl chloride (Vc) 2·5 gN-methoxymethyl propylene decylamine (n_mam) I21133. Doc -32- 200811200 3·5 g hydroxyethyl methacrylate 30.0 g dipropylene glycol 0.5 7.0 B) g dodecyl mercaptan g stearyl sulfhydryl / 11 oxidized ethyl adduct, F ion surfactant 4·〇g dodecyltrimethylammonium chloride (cationic interface surfactant B) 200·〇g water

After the emulsion was heated to 60 ° C, the mercaptopropane dihydrochloride salt. After the removal of excess vinyl chloride. Add g? hair conditioner 2, 2, _ azo-two 60. (The polymerization time was 6 hours. The dispersion obtained by the reaction had about 38% solid content'. The dispersion was acidified and diluted to 3 〇g/i. Coating on textile substrates. Textile was carried out as described in Example 33

Example 35: Preparation of Dispersion for Textile Surface Processing (Formulation 3) Second, to prepare a 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 gauge. 60·5 g fluoroalkyl acrylate (from Example 23) Temperature 12.5 g 2-ethylhexyl acrylate (2-EHAC) bO g vinylidene chloride (VDC) gN-methoxymethyl acrylamide 1 · 〇g methacrylic acid via ethyl ester 35.0 g dipropylene glycol 〇 · 7 g dodecyl mercaptan 6 · 0 g stearic acid thiol / 11 oxidative ethyl ester adduct (nonionic surfactant 121133.doc - 33 - 200811200 B) 5·0 g sodium dodecyl sulfate (SDS) 200·0 g water After the emulsion is heated to 60 ° C, add 0.5 g of initiator 2,2,-azo-di-2-methyl Mercaptopropane dihydrochloride. 6 The polymerization time at 〇 ° C is 6 hours. After the reaction, excess vinyl chloride was removed. The resulting dispersion had a solids content of about 36%. Acidizing and dispersing the dispersion

Cassurit HML (Cladant) and a 20 wt% aqueous solution of magnesium chloride were mixed so that the coating of the textile substrate was carried out in 30 lines per liter of liquid concentration under each condition. Examples 36-39: Preparation of a dispersion for textile surface processing as described in Example 33, Example 33. Example 40-43:

Similar to

Examples 44-47: For textile surface processing Example 3 5. Similar to the (oil) and water repellency (water) reports from Examples 33 to 47

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Claims (1)

200811200 X. Patent application scope: 1 · A fluorine-containing telomer compound of formula IV: RF-A-CH=CH(CH2)cCONR2(CH2)dZ (IV) wherein RF is perfluorocarbon having 1 to 2 carbon atoms Alkyl, A is a group of the formula: CF-2—CF-i «η CFrCXY, w — —CFrCXY —CF - L 1” ab a bi Ri L· | J R is CF3, 〇R3, Cl, Br or I, R2 is fluorene or an alkyl group having 1 to 4 carbon atoms, R3 is fluoromethyl, perfluoropropyl or perfluoropropoxypropyl, X and Υ is Η, C1 or F, Ζ is -ΟΗ, _OCOCH=CH2 or -〇COCCH3 = CH2, a is 0 to 10, ^^ is 1 to 30, and C and d are independently 1 to 11. 2. A compound as claimed in claim 1, characterized in that 1 is €1. 3. If requested! a compound characterized by r^CF3. 4. As requested! The compound is characterized in that χ and γ are F, or X is 卩 and ¥ is C1 ' or X and γ are hydrogen. 5. The compound of claim 1 which is characterized by 3 being 〇 to 5. 6. A compound according to claim 1, characterized in that 〇 and 4 are independently i, 2, 3, 7 or 8. A compound of the formula 1, which is characterized in that Rp is a polyfluoroalkyl group having up to 3 fluorinated carbon atoms. As claimed, the compound 'characterized by Rf is a polyfluoroalkyl group having 4 to 52 gas of carbon dioxide 121133.doc 200811200 atoms. 9. A compound according to claim 1 which is characterized in that the compound of formula IV has a molecular weight greater than 750 g/mol. 10. The compound of claim 1 which is characterized by a+b>3. A copolymer comprising a monomer of the formula IV of claim 1 (wherein z is -OCOCH^CHz or -0C0CCH3=CH2), one or more non-fluorinated polymerizable vinylic monomers, one or more Thermally crosslinked or isocyanate-reactive monomer and, optionally, chlorine-containing polymerizable vinylic monomer. 12 - a copolymer 'containing 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 the request Monomer, wherein Z is · OCOCH=CH2S-OCOCCH3=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) 0.5 wt% to 20 wt% and preferably 1 wt% to 10 wt% of one or more heat-crosslinkable or isocyanate-reactive monomers. 13. A copolymer comprising the following contents based on the total weight of the copolymer: a) 40 wt% to 99 wt% and preferably 45 wt% to 85 wt% of the formula IV of claim 1 a monomer, wherein z is -ococh=ch2 or -OCOCCH3=CH2, b) 0 wt% to 50 wt% and preferably 0.01 wt% to 30 wt% of one or more non-fluorine-containing polymerizable vinyl monomers and / or c) 15 wt% to 20 wt% and preferably 1 wt% to 10 wt% of one or more heat-crosslinkable or isocyanate-reactive monomers and 121133.doc 200811200 d) 0.5 wt% to 50 wt% and Preferably, from 2 wt% to 30 wt% of the chlorine-containing polymerizable ethylenic monomer. 14. Use of a copolymer according to any one of claims 11 to 13 for the water repellent, oil repellent and soil repellent surface treatment of fibrous substrates. 121133.doc 200811200 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-CH=CH(CH2)cCONR2(CH2)dZ (IV) 121133,doc