Mixture of fluorinated polyethers and use thereof as surfactant Number:7,141,537 from the United States Patent and Trademark Office (PTO) owispatent The present invention provides the use of a fluorinated polyether composition as a surfactant, said fluorinated polyether composition comprising a mixture of fluorinated polyethers of the formula: (R.sub.f).sub.n--X.sub.w--Z (I) wherein n is 1 or 2, w is 0 or 1, X is a divalent or trivalent organic linking group, Z is a polar group selected from the group consisting of an acid group or a salt thereof, an ammonium group, an amine-oxide group and an amphoteric group, and R.sub.f represents a perfluorinated polyether group of the formula: CF.sub.3CF.sub.2CF.sub.2--O--[CF(CF.sub.3)CF.sub.2O].sub.k--CF(CF.sub.3)-- - wherein k is at least 1; said mixture of fluorinated polyethers having a weight average molecular weight between 750 g/mol and 5000 g/mol and the amount of perfluorinated polyether groups in said mixture where k is 2 or less, is not more than 10% by weight of the total amount of perfluorinated polyether groups in said mixture.<H fluorinated, surfactant, Mixture, of, fluo, 7141537.html, Patent, pto, 7141537

Title: Mixture of fluorinated polyethers and use thereof as surfactant

Abstract: The present invention provides the use of a fluorinated polyether composition as a surfactant, said fluorinated polyether composition comprising a mixture of fluorinated polyethers of the formula: (R.sub.f).sub.n--X.sub.w--Z (I) wherein n is 1 or 2, w is 0 or 1, X is a divalent or trivalent organic linking group, Z is a polar group selected from the group consisting of an acid group or a salt thereof, an ammonium group, an amine-oxide group and an amphoteric group, and R.sub.f represents a perfluorinated polyether group of the formula: CF.sub.3CF.sub.2CF.sub.2--O--[CF(CF.sub.3)CF.sub.2O].sub.k--CF(CF.sub.3)-- - wherein k is at least 1; said mixture of fluorinated polyethers having a weight average molecular weight between 750 g/mol and 5000 g/mol and the amount of perfluorinated polyether groups in said mixture where k is 2 or less, is not more than 10% by weight of the total amount of perfluorinated polyether groups in said mixture.

Patent Number: 7,141,537 Issued on 11/28/2006 to Audenaert, et al.

Inventors: Audenaert; Frans A. (Kaprijke, BE), Dams; Rudolf J. (Antwerp, BE), Tan; Lian S. (Woodbury, MN)
Assignee: 3M Innovative Properties Company (St. Paul, MN)

Appl. No.: 10/696,950

Filed: October 30, 2003

Current U.S. Class: 510/356 ; 562/587

Current International Class: C11D 17/00 (20060101)

Field of Search: 510/356 562/587

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Primary Examiner: Page; Thurman K.
Assistant Examiner: Nwaonicha; Chukwuma

Claims

What is claimed is:

1. A composition comprising an organic or aqueous liquid having dissolved or dispersed therein a mixture of fluorinated polyethers of the formula: (R.sub.f).sub.n--X.sub.w--Z wherein n is 1 or 2, w is 0 or 1, X is a divalent or trivalent organic linking group, Z is a polar group selected from the group consisting of an acid group or salt thereof, an ammonium group, an amine-oxide group and an amphoteric group, and R.sub.f represents a perfluorinated polyether group of the formula: CF.sub.3CF.sub.2CF.sub.2--O--[CF(CF.sub.3)CF.sub.2O].sub.k--CF(CF.sub.3)-- - wherein k is at least 1; said mixture of fluorinated polyethers having a weight average molecular weight between 750 g/mol and 5000 g/mol and the amount of perfluorinated polyether groups in said mixture where k is 2 or less, is not more than 10% by weight of the total amount of perfluorinated polyether groups in said mixture.

2. The composition according to claim 1, wherein the organic liquid is selected from the group consisting of polar solvents selected from the group consisting of alcohols, ketones, esters, ethers and amides, non-polar solvents selected from the group consisting of aromatic and aliphatic hydrocarbon solvents and halogenated solvents selected from the group consisting of hydrofluoroethers, hydrofluorocarbons and chlorinated hydrocarbons.

3. The composition according to claim 1, wherein the organic linking group corresponds to the formula --CONR.sup.8--(CH.sub.2).sub.s--, wherein R.sup.u is hydrogen or C.sub.1-6-alkyl or C.sub.1-6-kyl substituted by halogen, OH, or SH and s is 1 to 20.

4. The composition according to claim 1, wherein Z corresponds to the formula: ##STR00003## wherein each of R.sup.1, R.sup.2 and R.sup.3 independently represents a hydrogen atom or a hydrocarbon group that may optionally be substituted, M represents a counter ion, r is 0 or 1, and when r is 0, one of R.sup.1, R.sup.2 and R.sup.3 represents a hydrocarbon group that is substituted with an acid group or wherein Z corresponds to the formula: ##STR00004## wherein R.sup.4 and R.sup.3 are independently C.sub.1-6-alkyl, C.sub.1-6-alkyl substituted by a halogen, a C.sub.1-6-alkoxy, NO.sub.2 or CN group, or R.sup.4 and R.sup.5 join to form a 5 to 7 menibered ring that may contain one or more additional hetero atoms and that may be substituted by one or more C.sub.1-6-alkyl groups.

5. The composition according to claim 1 further comprising one or monomers capable of polymerization.

6. The composition according to claim 1 further comprising a fluorochemical compound capable of providing oil- and/or water repellency properties to a substrate.

7. A mixture of fluorinated polyethers of the formula: (R.sub.r).sub.n--X.sub.w--Z wherein n is 1 or 2, w is 0 or 1, X is a divalent or trivalent organic linking group, Z is a polar group selected from the group consisting of an ammonium group, an amine-oxide group and an amphoteric group, and R.sub.f represents a perfluorinated polyether group of the formula: CF.sub.3CF.sub.2CF.sub.2--O--[CF(CF.sub.3)CF.sub.2O].sub.k--CF(CF.sub.3)-- - wherein k is at least 1; said mixture of fluorinated polyethers having a weight average molecular weight between 750 g/mol and 5000 g/mol and the amount of perfluorinated polyether groups in said mixture where k is 2 or less, is not more than 10% by weight of the total amount of perfluorinated polyether groups in said mixture.

8. A method of altering the surface energy and/or interfacial free energy of a medium, said method comprising 1) providing a medium and 2) incorporating a fluorinated polyether composition therein, said fluorinated polyether composition comprising a mixture of fluorinated polyethers of the formula: (R.sub.f).sub.n--X.sub.w--Z wherein n is 1 or 2, w is 0 or 1, X is a divalent or trivalent organic linking group, Z is a polar group selected from the group consisting of an acid group or a salt thereof, an ammonium group, an amine-oxide group and an amphoteric group, and R.sub.f represents a perfluorinated polyether group of the formula: CF.sub.3CF.sub.2CF.sub.2--O--[CF(CF.sub.3)CF.sub.2O].sub.k--CF(- CF.sub.3)-- wherein k is at least 1 ; said mixture of fluorinated polyethers having a weight average molecular wcight between 750 g/mol and 5000 g/mol and the amount of perfluorinated polyether groups in said mixture where k is 2 or less, is not more than 10% by weight of the total amount of perfluorinated polyether groups in said mixture.

9. The method of claim 8, wherein the organic linking group corresponds to the formula --CONR.sup.6--(CH.sub.2).sub.9--, wherein R.sup.a is hydrogen or C.sub.1-6-alkyl or C.sub.1-6-alkyl substituted by halogen, OH, or SH, and s is 1 to 20.

10. The method of claim 8, wherein Z corresponds to the formula: ##STR00005## wherein each of R.sup.1, R.sup.2 and R.sup.3 independently represents a hydrogen atom or a hydrocarbon group that may optionally be substituted, M represents a counter ion, r is 0 or 1, and when r is 0, one of R.sup.1, R.sup.2, and R.sup.3 represents a hydrocarbon group that is substituted with an acid group or wherein Z corresponds to the formula: ##STR00006## wherein R.sup.4 and R.sup.5 are independently C.sub.1-6-alkyl, C.sub.1-6-alkyl substituted by a halogen, a C.sub.1-6-alkoxy, NO.sub.2, or CN group, or R.sup.4 and R.sup.5 join to form a 5 to 7 memberod ring that may contain one or more additional hetero atoms and that may be substituted by one or more C.sub.1-6-alkyl groups.

11. The method of claim 8, wherein said medium is a coating composition or fire-fighting agent.

Description

FIELD OF THE INVENTION

The invention relates to the use of a particular fluorinated polyether composition as a surfactant. The invention also relates to a composition comprising an organic or aqueous liquid having dissolved or dispersed therein a mixture of fluorinated polyethers. The invention further relates to a mixture of fluorinated polyethers.

BACKGROUND

Fluorinated polyethers are well-known in the art and have found many applications. For example, fluorinated polyethers and their use have been described in U.S. Pat. Nos. 3,250,808, 3,839,425, and 5,130,477. The fluorinated polyethers have been used as intermediates in the preparation of useful compositions to be applied to substrates to impart oil and/or water repellent properties. The fluorinated polyethers have also been used as surfactants and emulsifying compounds. For example, fluoropolyether acids, amides and salts thereof have been described in U.S. Pat. Nos. 3,644,492, 3,798,265, 3,555,089, 3,621,059, 3,944,610, and 3,536,710.

There is however an ever growing environmental awareness and the fluorinated polyethers disclosed in the art, in particular those that have been disclosed for use as surfactants, may no longer meet today's expectations with respect to the environmental properties and impact of compositions based on such polyethers. It is a particularly desired environmental property that the fluorochemical surfactants are substantially free of fluorochemical components that eliminate slowly from the body of living organisms. Additionally, it is desired that the fluorochemical surfactants have a sufficient stability under normal conditions of use and storage such that they do not decompose into fluorochemical components that eliminate slowly from the body of living organisms. Of course in seeking more environmentally friendly compositions, other properties such as the performance as surfactants in a broad variety of applications should not be compromised or at least not to a substantial level and preferably the compositions can be conveniently manufactured at minimal costs.

SUMMARY OF THE INVENTION

The invention provides in one aspect the use of a fluorinated polyether composition as a surfactant, said fluorinated polyether composition comprising a mixture of fluorinated polyethers of the formula: (R.sub.f).sub.n--X.sub.w--Z (I) wherein n is 1 or 2, w is 0 or 1, X is a divalent or trivalent organic linking group, Z is a polar group selected from the group consisting of an acid group or a salt thereof, an ammonium group, an amine-oxide group and an amphoteric group, and R.sub.f represents a perfluorinated polyether group of the formula: CF.sub.3CF.sub.2CF.sub.2--O--[CF(CF.sub.3)CF.sub.2O].sub.k--CF(CF.sub.3)-- - wherein k is at least 1; said mixture of fluorinated polyethers having a weight average molecular weight between 750 g/mol and 5000 g/mol and the amount of perfluorinated polyether groups in said mixture where k is 2 or less, is not more than 10% by weight of the total amount of perfluorinated polyether groups in said mixture.

By the term surfactant is meant "a substance that, when present at low concentration in a system, has the property of adsorbing onto the surfaces or interfaces of the system and of altering to a marked degree the surface or interfacial free energies of these surfaces." (Milton J. Rosen, "Surfactants and Interfacial Phenomena," Second Ed., John Wiley & Sons, New York, N.Y., 1989, page 1). The fluorinated polyether compositions according to the invention have been found to have these properties. In one aspect, the invention provides a method for altering, e.g., lowering, the surface energy and/or interfacial free energy, of a medium, the method comprising providing a medium and incorporating, e.g., dissolving, a fluorinated polyether composition as described herein in the medium.

In another aspect, the invention provides a composition comprising an organic or aqueous liquid having dissolved or dispersed therein a mixture of fluorinated polyethers as defined above.

In still a further aspect, the invention relates to a composition as described above, further comprising one or monomers capable of polymerization. A further aspect of the invention relates to a composition as described above, further comprising a fluorochemical compound capable of providing oil- and/or water repellency properties to a substrate. In yet another aspect the invention provides for a use of a composition as described above as a coating composition or fire-fighting agent.

In a further aspect, the invention provides for a mixture of fluorinated polyethers of the formula: (R.sub.f).sub.n--X.sub.w--Z (I) wherein n is 1 or 2, w is 0 or 1, X is a divalent or trivalent organic linking group, Z is a polar group selected from the group consisting of an ammonium group, an amine-oxide group and an amphoteric group, and R.sub.f represents a perfluorinated polyether group of the formula: CF.sub.3CF.sub.2CF.sub.2--O--[CF(CF.sub.3)CF.sub.2O].sub.k--CF(CF.sub.3)-- - wherein k is at least 1; said mixture of fluorinated polyethers having a weight average molecular weight between 750 g/mol and 5000 g/mol and the amount of perfluorinated polyether groups in said mixture where k is 2 or less, is not more than 10% by weight of the total amount of perfluorinated polyether groups in said mixture.

It has been found that compositions comprising fluorinated polyethers or mixtures thereof, having a molecular weight between 750 g/mol and 5000 g/mol provide compositions having good or excellent environmental properties combined with good or excellent surfactant properties. In particular, the surfactant properties are such that the surfactants can be used in a wide variety of applications. Furthermore, the compositions may be prepared without processing difficulties and the fluorinated polyethers or mixtures thereof can readily be dissolved or dispersed in water or an organic solvent or mixtures thereof.

The fluorinated polyether components of the compositions that have a perfluorinated polyether moiety having a molecular weight of at least 750 g/mol eliminate effectively from the body of living organisms and should not normally produce, under normal storage and use conditions, degradation products that cannot be effectively eliminated from the body of living organisms.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS OF THE INVENTION

The R.sub.f group in formula I represents a perfluorinated polyether group of formula: CF.sub.3CF.sub.2CF.sub.2--O--[CF(CF.sub.3)CF.sub.2O].sub.k--CF(CF.sub.3)-- - wherein k is at least 1 and can be derived from the oligomerization of hexafluoropropylene oxide. It will be evident to one skilled in the art that mixtures of perfluorinated polyether groups will be formed. In a preferred embodiment, k is an integer of 3 to 25. When k equals 3, the perfluorinated polyether group has a molecular weight of 783. In a preferred embodiment the amount of perfluorinated polyether groups in said mixture where k is 2 or less, is not more than 10% by weight of the total amount of perfluorinated polyether groups in said mixture. More preferably, the amount of perfluorinated polyether groups in said mixture where k is 2 or less is not more than 5% by weight, most preferably not more than 1% by weight based on the total weight of perfluorinated polyether moieties in the composition. The lower the amount of perfluorinated polyether groups having a molecular weight of less than 750 g/mol, the better the environmental properties of the resulting composition will generally be.

Examples of organic linking groups X include non-fluorinated organic groups that comprise aromatic or aliphatic groups that may be interrupted by O, N, or S and that may be substituted, alkylene groups, oxy groups, thio groups, urethane groups, carboxy groups, carbonyl groups, amido groups, oxyalkylene groups, thioalkylene groups, carboxyalkylene, and/or amidoalkylene groups.

Typical examples of X include --CONR.sup.a--(CH.sub.2).sub.s--, wherein R.sup.a is hydrogen or C.sub.1-6-alkyl or C.sub.1-6-alkyl substituted by halogen, OH, or SH; and s is 1 to 20. Preferred examples of X further include --CH.sub.2O(CH.sub.2).sub.s--, --C(O)O(CH.sub.2).sub.s--, --C(O)S(CH.sub.2).sub.s--, --O(CH.sub.2).sub.sand --CO[NHCH.sub.2CH.sub.2]NH.sub.uCO-- where u is 1 to 4; s is 1 to 20. A particularly useful linking group X is --CONH(CH.sub.2).sub.3--.

The polar group Z can be selected from the group consisting of an acid group or salt thereof, an ammonium group, an amine-oxide group and an amphoteric group. In a particular preferred embodiment, the group Z can be represented by the formula:

##STR00001## wherein each of R.sup.1, R.sup.2 and R.sup.3 independently represents a hydrogen atom or a hydrocarbon group that may optionally be substituted, M represents a counter ion, r is 0 or 1 and when r is 0, one of R.sup.1, R.sup.2 and R.sup.3 represents a hydrocarbon group that is substituted with an acid group, such as for example --CH.sub.2CH.sub.2CH.sub.2SO.sub.3.sup.-.

Representative examples of M include Cl.sup.-, CH.sub.3COO.sup.-, C.sub.2H.sub.5SO.sub.4.sup.-, I.sup.-, Br.sup.-, CF.sub.3SO.sub.3.sup.-, 1/2SO.sub.4.sup.2-.

In a further preferred embodiment, the group Z corresponds to the formula:

##STR00002## wherein R.sup.4 and R.sup.5 are independently C.sub.1-6-alkyl, C.sub.1-6-alkyl substituted by halogen, C.sub.1-6-alkoxy, NO.sub.2 or CN, or R.sup.4 and R.sup.5 may join to form a 5 to 7 membered ring that may contain one or more additional hetero atoms and that may be substituted by one or more C.sub.1-6-alkyl groups.

Compounds according to formula (I) can conveniently be prepared through oligomerization of hexafluoropropylene oxide (HFPO), which results in a perfluoropolyether carbonyl fluoride. This carbonyl fluoride may be converted into an acid, ester or alcohol by reactions well known to those skilled in the art. The carbonyl fluoride, acid, ester or alcohol derived therefrom may then be reacted further to introduce the desired groups according to known procedures. For example, EP 870 778 describes suitable methods to produce compounds according to formula (I) having desired Q Z moieties. For example quaternary ammonium compounds according to formula II can be prepared by reacting the fluorinated polyether ester compound, with an amine, such as, e.g., 3-(dimethylamino)-propylamine. The amine compound can further be quaternized through reaction with an acid, such as hydrochloric acid or acetic acid or alkylating agents, such as diethylsulfate, propane sultone, methyliodide, butylbromide or methylchloride. The fluorinated amine-oxide surfactants, according to formula III can be prepared by treating the fluorinated amine precursor with hydrogen peroxide or peracid, such as perbenzoic acid or peracetic acid. This reaction may be carried out at elevated temperatures, for example at about 60.degree. C. to 70.degree. C.

The method of making the fluorinated polyether surfactants according to formula (I) will result in a mixture of fluorinated polyethers that have different molecular weights. The molecular weight range of the surfactants can be tailored via fractional distillation of the fluorinated polyether acid fluoride or ester precursor. In a preferred embodiment, such a mixture of fluorinated polyether compounds according to formula (I) contains fluorinated polyether compounds having a perfluorinated polyether moiety having a molecular weight of less than 750 g/mol in an amount of not more than 10% by weight relative to total weight of fluorinated polyether compounds, preferably not more than 5% by weight and most preferably not more than 1% by weight. The fluorinated surfactants typically will have a weight average molecular weight such that it is readily dissolved or dispersed in water or an organic solvent or mixtures thereof. Generally, the weight average molecular weight of the fluorinated polyether is not more than 5000 g/mol, preferably not more than 4000 g/mol with a typical range being between 750 g/mol and 2500 g/mol.

The mixture of fluorinated polyethers can be dispersed or dissolved in water or an organic liquid or mixtures thereof. Organic liquids that can be used in the fluorinated polyether compositions include aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, cyclohexane), aromatic solvents (e.g., benzene, toluene, xylene), ethers (e.g., diethylether, glyme, diglyme, diisopropyl ether), alkoxy alkylene ethers (e.g. dipropylene glycol monomethylether, triethyleneglycol), esters (e.g., ethyl acetate, butyl acetate), alcohols (e.g., ethanol, isopropyl alcohol), ketones (e.g., acetone, methylethyl ketone, methyl isobutyl ketone), sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone), halogenated solvents selected from the group consisting of hydrofluoroethers, hydrofluorocarbons and chlorinated solvents, such as methylchloroform, FREON.TM. 113, trichloroethylene, .alpha.,.alpha.,.alpha.-trifluorotoluene, and mixtures thereof.

The mixture of fluorinated polyethers has been found to have good or excellent surfactant properties such that the mixture can be used in a wide variety of applications where surfactant properties are desired and/or needed. In particular, the mixture of fluorinated polyethers is very effective in reducing the surface tension of liquids. Similarly, the mixture can improve the wetting of a surface of a substrate by a liquid or coating mixture.

In one embodiment, a composition comprising the mixture of fluorinated polyethers can be used as an emulsifying agent or stabilizer in emulsion or dispersion polymerization of one or more monomers.

In a particular embodiment, the mixture of fluorinated polyethers can act as a surfactant in an aqueous emulsion polymerization of fluorinated monomers (fluoromonomers) with optional fluorinated and non-fluorinated comonomers to form fluoropolymers. The fluoropolymers may have a partially fluorinated backbone, generally at least 40% by weight fluorinated, or a fully fluorinated backbone. Examples of fluoromonomers include fluorinated ethylenically-unsaturated monomers such as, for example, tetrafluoroethylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropene, vinyl fluoride, and pentafluoropropene. Optional comonomers include perfluorovinyl ethers such as perfluoro(methyl vinyl) ether, perfluoro(methoxyethyl vinyl) ether, perfluoro (propyl vinyl) ether, perfluoro (2-(n-propoxy)propyl vinyl) ether, and perfluoro(ethoxyethyl vinyl) ether, Examples of non-fluorinated comonomers include ethylene and propylene.

Processes for polymerizing fluorinated monomers as described above, with optional comonomers in aqueous media are well known and described for example in U.S. Pat. Nos. 3,271,341, 6,395,848 and 6,429,258, EP 0 625 526, and WO 02/095121. The mixture of fluorinated polyethers can be used in these processes as an alternative for the fluorinated surfactants described in these references. While the known emulsion polymerization process of fluoromonomers has typically been carried out with anionic fluorinated surfactants, the mixture of fluorinated polyethers that can be used in the emulsion polymerization process is not limited to mixtures of anionic fluorinated polyethers. Indeed it has been found that also cationic fluorinated polyether mixtures can be used in the aqueous emulsion polymerization. This offers the advantage that also cationically stabilized fluoropolymer dispersions can be produced in a convenient way. Generally, the mixture of fluorinated polyethers should be used in amounts between 0.5% and 10% by weight, based on the total weight of the monomers present and the emulsion polymerization of the fluoromonomers can be conducted in the known and common way.

Typically the emulsion polymerization is carried out in the presence of a free radical initiator. Typically utilized free radical initiators include diisopropyl peroxydicarbonate and permanganate compounds of the formula QMnO.sub.4 where Q is hydrogen, ammonium, alkali earth metal, or alkaline earth metal or a redox system such as hydrogen peroxide/ascorbic acid combinations. One or more chain transfer agents, such as isopropyl alcohol, may also be used to control the molecular weight of the polymer. Polymerization may be effected by mixing the foregoing ingredients in aqueous media at a temperature typically between about 50 and 125.degree. C. and a pressure typically between about 7 and 40 kg/cm.sup.2 and generally is carried out in a gently stirred autoclave.

In yet another embodiment, the fluorinated polyether surfactant compositions can be used as a stabiliser in the polymerization of fluorochemical monomers, having a fluorinated group and an ethylenically unsaturated group free of fluorine, and optional non-fluorinated comonomers. It has been found that the mixture of fluorinated polyethers acts as an effective emulsifier or surfactant in the emulsion polymerization such that emulsions of good stability are obtained together with a high yield of polymer solids.

In a particular embodiment, the fluorochemical monomers correspond to the general formula: R.sup.2.sub.f--Q.sup.1--E.sup.1 (IV) wherein R.sup.2.sub.f represents a fluoroaliphatic group containing at least 3 carbon atoms or a fluorinated polyether group. Q.sup.1 represents an organic divalent linking group, typically an non-fluorinated group and E.sup.1 represents a non-fluorinated free radical polymerizable group.

The fluorinated monomer is typically an ester of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid and contains a fluoroaliphatic group. Examples of fluorochemical monomers include: CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OCOCR.sup.1.dbd.CH.sub.2 CF.sub.3(CF.sub.2).sub.2CH.sub.2OCOCR.sup.1.dbd.CH.sub.2 CF.sub.3(CF.sub.2).sub.3SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OCOCR.sup.1.db- d.CH.sub.2 CF.sub.3(CF.sub.2).sub.3SO.sub.2N(C.sub.2H.sub.5)CH.sub.2CH.sub.2OCOCR.su- p.1.dbd.CH.sub.2 CF.sub.3(CF.sub.2).sub.3SO.sub.2N(CH.sub.3)CH.sub.2CH(CH.sub.3)OCOCR.sup.- 1.dbd.CH.sub.2 and (CF.sub.3).sub.2CFCF.sub.2SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OCOCR.sup.1.- dbd.CH.sub.2 wherein R.sup.1 is hydrogen or methyl.

The non-fluorinated comonomer is typically a monomer comprising a polymerizable group and a hydrocarbon group, which may optionally be substituted. For example the non-fluorinated monomer may be a hydrocarbon group containing monomer having an aliphatic group of 1 to 30 carbon atoms and an ethylenically unsaturated group. The hydrocarbon group is preferably selected from the group consisting of a linear, branched or cyclic alkyl group, an aralkyl group, an alkylaryl group and an aryl group. Typical examples of non-fluorinated monomers include those selected from isobutyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl methacrylate, lauryl (meth)acrylate, methyl methacrylate, octadecyl(meth)acrylate, N-hydroxymethyl acrylamide, methoxy polyethyleneglycol methacrylate, N-hydroxymethyl acrylamide and urethane (meth)acrylate type monomers. Further non-fluorinated comonomers include for example chlorine containing monomers, such as, e.g., vinylchloride and vinylidene chloride.

Typically the polymerization is a free radical polymerization. The surfactants can be used alone or in combination with further co-surfactants. Alternatively, the polymerization may be done in an organic solvent, followed by a post-emulsification using the mixture of fluorinated polyethers as stabilizer.

Free radical polymerization of the above fluorochemical monomers optionally in combination with one or more non-fluorinated monomers can be thermally or photochemically initiated by use of a free radical initiator. Useful free radical initiators are known in the art and include azo compounds, such as azobisisobutyronitrile (AIBN), azobisvaleronitrile and azobis(2-cyanovaleric acid), 2,2'-azobis(2-amidinopropane)dihydrochloride and the like, hydroperoxides such as cumene, t-butyl, and t-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl and dicumylperoxide, peroxyesters such as t-butylperbenzoate and di-t-butylperoxy phtalate, diacylperoxides such as benzoyl peroxide and lauroyl peroxide.

The polymerisation may further be carried out in the presence of a chain transfer agent or a chain terminator to tailor the molecular weight and/or properties of the resulting fluorinated copolymer.

In order to stabilise the polymerization medium, the mixture of fluorinated polyethers will typically be added in amounts between about 1% and 15% by weight based on the total weight of the monomers present.

In a further embodiment, the mixture of fluorinated polyethers is used as a surfactant in compositions comprising an aqueous or organic solvent and a fluorochemical compound capable of providing oil- and/or water repellency properties. The mixture of fluorinated polyethers may be dispersed or dissolved in the composition and is typically used in these compositions to obtain a homogeneous and stable mixture of the fluorochemical compound. Such a composition can be used to provide oil- and water repellent properties to a substrate including for example fibrous substrates as well as hard surfaces such as glass or ceramic articles.

Examples of fluorochemical compounds suitable for providing oil- and/or water repellency properties include fluorochemical acrylates and methacrylates, as may be obtained as described above or as taught for example in EP 1329548, fluorochemical urethanes as described in for example U.S. Pat. No. 5,910,557, fluorochemical esters as described in, for example, U.S. Pat. Nos. 6,288,157 and 6,525,127 and fluoropolymers as is taught in for example WO 02/095121.

The fluorochemical treatment composition comprising a fluorochemical compound and the mixture of fluorinated polyethers can be applied to a substrate. The substrates that can be treated by the fluorochemical composition are not especially limited and include for example fibrous substrates, such as textile and carpet. The fibrous substrate may be based on synthetic fibers, e.g., polyester, polyamide and polyacrylate fibers or natural fibers, e.g., cellulose fibers as well as mixtures thereof. The fibrous substrate may be a woven as well as a non-woven substrate. The treated substrates have good repellency properties, in particular the treated substrates are readily repellent to water and oils.

The mixture of fluorinated polyethers should generally be used in amounts effective to obtain a stable treatment composition. However the amount of the mixture of fluorinated polyethers is preferably kept as low as possible so as to not adversely affect the repellent properties. It has been found that the mixture of fluorinated polyethers is highly effective in obtaining compositions of desired stability even at low amounts. Typically the mixture of fluorinated polyethers may be used in amounts between 1% and 15%, preferably between 2% and 10%, by weight based on the total solids weight.

In a further particular embodiment of the present invention, a composition comprising the mixture of fluorinated polyethers and a fluorochemical compound can be used as a treatment composition to render substrates, having a hard surface, such as ceramics or glass, oil and water repellent.

Fluorochemical compounds suitable for use in such a treatment composition for hard surfaces are typically fluorosilanes. Fluorosilanes typically comprise one or more fluorinated groups and one or more silyl groups having one or more hydrolyzable groups. By the term "hydrolyzable group" is meant that the groups are capable of hydrolyzing under the conditions used to prepare the fluorinated treatment composition and/or the conditions to apply the fluorinated composition to the substrate. Such conditions may involve the use of a catalyst such as an acid or base. Examples of suitable hydrolyzable groups include alkoxy groups, aryloxy groups, halogens such as chlorine, acetoxy groups and acyl groups. Generally preferred are lower alkoxy groups having 1 to 4 carbon atoms.

The fluorosilane may contain one or more, for example, two or three, silane groups linked directly to a fluorinated group or they may be linked to a fluorinated group through an organic linking group. Such an organic linking group is generally a non-fluorinated group such as a hydrocarbon group and may contain one or more heteroatoms.

The fluorosilane may comprise one or more fluorinated groups including fluoroaliphatic groups and fluorinated polyether groups. The fluorinated group(s) of the fluorosilane may be partially or fully fluorinated and may be monovalent or multivalent, e.g., divalent.

Examples of preferred fluorosilanes include, but are not limited to, the following approximate average structures: ACF.sub.2O(CF.sub.2O).sub.m(C.sub.2F.sub.4O).sub.pCF.sub.2A, C.sub.3F.sub.7O(CF(CF.sub.3)CF.sub.2O).sub.pCF(CF.sub.3)A, ACF(CF.sub.3)O(CF(CF.sub.3)CF.sub.2O).sub.pCF(CF.sub.3)A, ACF.sub.2O(C.sub.2F.sub.4O).sub.pCF.sub.2A, CF.sub.3O(C.sub.2F.sub.4O).sub.pCF.sub.2A, and A(CF.sub.2).sub.3O(C.sub.4F.sub.8O).sub.p(CF.sub.2).sub.3A, wherein --A is --B--SiY.sub.3-x.sup.1R.sub.x, B represents an organic linking group, Y.sup.1 is a hydrolysable group and R represents a C.sub.1 C.sub.4 alkyl group, x is 0, 1 or 2 and an average value for m and p is 0 to 50, with the proviso that m and p are not simultaneously 0. The values of m and p in these approximate average structures can vary. Preferably, an average value of m is within a range of about 1 to about 50, and an average value of p is within a range of about 4 to about 40.

Fluorinated compounds including fluoropolyether groups are taught for example in U.S. Pat. Nos. 6,613,860; 6,592,659 and published US application no. 2003/0113555.

The compositions used for the treatment of hard surfaces may also include an acid or base catalyst. The acid catalyst, if present, comprises an organic or inorganic acid. Organic acids include acetic acid, citric acid, formic acid and the like. Examples of inorganic acids include sulphuric acid, hydrochloric acid and the like. The acid will generally be included in the composition in an amount between about 0.01 and 10%, more preferably between 0.05 and 5% by weight. The base catalyst, if present, comprises for example sodium or potassium hydroxide or an amine containing compound.

The treatment composition may further comprise one or more auxiliary compounds of an element M.sup.2 selected from the group consisting of Si, Ti, Zr, B, Al, Ge, V, Pb and Sn and having at least two hydrolysable groups per molecule in an amount sufficient to form a polycondensation product upon reaction with said fluorochemical oligomer. Examples include tetramethoxysilane, tetra ethoxysilane, methyl triethoxysilane, dimethyldiethoxysilane, octadecyltriethoxysilane, methyl trichlorosilane, tetra-methyl orthotitanate, tetra ethyl orthotitanate, tetra-iso-propyl orthotitanate, tetra-n-propyl orthotitanate, tetraethyl zirconate, tetra-iso-propyl zirconate tetra-n-propyl zirconate and the like.

The treatment composition is typically a solution or dispersion in water and can be applied to the substrates by methods known in the art and described for example in U.S. Pat. Nos. 6,613,860 and 6,592,659 and U.S. patent application No. 2003/0113555.

Suitable substrates that can be treated in a particularly effective way with the fluorinated composition comprising an organic or aqueous liquid having dissolved or dispersed therein a mixture of fluorinated polyethers and a fluorosilane, include substrates having a hard surface that preferably has groups capable of reacting with the fluorosilane. Particularly preferred substrates include ceramics, glass, metal, natural and man-made stone and wood.

In still further embodiment, the mixture of fluorinated polyethers can be used in fire fighting formulations for fighting polar and non-polar fuel and solvent fires. Fire fighting concentrates typically comprise fluorinated surfactants, fluorine-free surfactants, foam stabilizers, and optional further additives.

These concentrates typically are designated as 1%, 3%, or 6% concentrates and are diluted with 99%, 97%, or 94% fresh or sea water respectively to form a premix. The premix must exhibit good foaming characteristics to produce a thick foam blanket that achieves rapid knock down, control, extinguishment, and resistance to reignition of the fire and persists for a significant time after the fire's extinguishment. The surfactants detailed herein find particular