ETHERS

FIELD

[0001] The present disclosure relates to copolymers of vinylidene fluoride and at least one perfluoro(allyl ether). These copolymers are essentially free of cure site groups.

SUMMARY

[0002] Briefly, in one aspect, the present disclosure provides a fluoropolymer comprising 20 to 90 mole percent e.g., 30 to 50 mole percent vinylidene fluoride; and 10 to 45 mole percent, e.g., 15 to 30 mole percent of one or more perfluorinated allyl ethers, wherein the fluoropolymer comprises no greater than 5 parts per million (ppm), e.g., no greater than 1 ppm, by weight of curesite groups based on the total weight of the fluoropolymer. In some embodiments, the fluoropolymer comprises 20 to 80 weight percent, e.g., 25 to 60 weight percent, of the one or more perfluorinated allyl ethers.

[0003] In some embodiments, the perfluorinated allyl ethers are selected from the group consisting of perfluorinated allyl ethers according to Formula 1:

CF ₂ =CF-CF2-0-(CF2) _m -0 _p -(CF ₂ ) _n -F wherein: m = 1 to 6, p is 0 or 1, and n = 0 to 6, provided that when p is 1, n is not 0. For example, in some embodiments, at least one allyl ether is selected from the group consisting of perfluorinated allyl ethers according to Formula 1, wherein p and n are 0:

CF ₂ =CF-CF ₂ -0-(CF ₂ ) _m -F.

In some embodiments, at least one allyl ether is selected from the group consisting of perfluorinated allyl ethers according to Formula 1, wherein p is 1 and n is 1 to 6:

CF2=CF-CF ₂ -0-(CF2) _m -0-(CF ₂ ) _n -F.

[0004] In some embodiments, the fluoropolymer comprises at least one perfluorinated alkyl vinyl ether, e.g., at least 1 mole percent perfluorinated alkyl vinyl ether. In some embodiments, the fluoropolymer comprises no greater than 20 mole percent of perfluorinated alkyl vinyl ethers, preferably no greater than 10 mole percent of perfluorinated alkyl vinyl ethers. In some embodiments,

perfluorinated alkyl vinyl ethers are selected from the group consisting of perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and combinations thereof, optionally wherein the perfluoroalkyl vinyl ether is perfluoro(methyl vinyl ether).

[0005] In some embodiments, the fluoropolymer has a glass transition temperature of no greater than

20 °C, preferably no greater than 0 °C, as measured according to Tg Method. In some embodiments, the fluoropolymer has a Mooney viscosity at 121 °C of from 1 to 150, as measured according to Mooney

Viscosity Method.

[0006] In some embodiments, the fluoropolymer comprises less than 1 part per million of

perfluorinated alkanoic acids with 6 to 20 carbon atoms based on the weight of polymer.

[0007] In another aspect, the present disclosure provides an article comprising the fluoropolymer according to any of the embodiments of the present disclosure. In some embodiments, the article comprises a surface and a layer comprising the fluoropolymer covering at least a portion of the surface.

In some embodiments, the article comprises a porous substrate and the fluoropolymer is at least partially infused in the substrate.

[0008] In another aspect, the present disclosure provides a coating comprising a solvent and the fluoropolymer according to any of the embodiments of the present disclosure dissolved or dispersed in the solvent. In some embodiments, the fluoropolymer is dispersed in the solvent and the solvent comprises water. In some embodiments, such water-based coatings further comprise a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, or combinations thereof. In some embodiments, the fluoropolymer is dissolved in the solvent and the solvent comprises at least one fluorinated solvent.

[0009] The above summary of the present disclosure is not intended to describe each embodiment of the present invention. The details of one or more embodiments of the invention are also set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.

DETAILED DESCRIPTION

[0010] Materials providing oil-, water-, or dirt-repellency are desired in many applications including for use with clothing, appliance, and architectural applications. Fluorinated (meth)acrylate-based materials have been used; however, the fluorinated side chains can be hydrolyzed leading to a degradation in performance. Hexafluoropropylene oxide (HFPO) oligomers have been used, but with limited success.

[0011] Perfluorinated copolymers of tetrafluoroethylene (TFE) and perfluoro(alkyl vinyl ethers)

(PAVE) may provide the desired performance. However, as short chain PAVEs such a perfluoro(methyl vinyl ether) (PMVE) do not provide the desired performance, longer chain PAVEs such as

perfluoro(propyl vinyl ether) (PPVE) must be used. Such longer chain PAVEs can generate undesirable amounts of perfluorinated carboxylic acids (PFCAs) during polymerization. For example, levels of C7 to C 14 PFCAs greater than 10 ppm may be generated. The removal of the PFCA's to acceptable levels (e.g. < 200 ppb) is quite difficult and expensive, and may not always be possible.

[0012] Crosslinked elastomers based on copolymers of vinylidene fluoride (VDF) and perfluoro(allyl ethers) are known. However, such materials generally swell in solvents rather than dissolving or dispersing in solvents to form coatings. [0013] European Patent Number EP 1 838 742B1 (“Fluoropolymer for Making a Fluoroelastomer”) is directed to an amorphous fluoropolymer that comprises one or more cure sites and one or more repeating units deriving from a fluorinated allyl ether.

[0014] European Patent Application Number EP 2 868 674A1 (“Peroxide Curable Fluoropolymers Obtainable by Polymerization Using Non-Fluorinated Polyhydroxy Emulsifiers”) describes methods of making curable fluoropolymers comprising repeating units derived from VDF and at least one perfluorinated monomer using one or more chain transfer agents containing one or more halogens selected from iodine, bromine, or a combination thereof.

[0015] Surprisingly, the present inventors discovered that copolymers of vinylidene fluoride (VDF) with greater than 10 mole percent perfluoro(allyl ether) (“PAE”) can provide one or more significant benefits. As used herein, a copolymer of VDF and PAE refers to copolymers resulting from the copolymerization of VDF and one or more PAEs, and optionally, one or more other comonomers. Thus, a copolymer of VDF and PAE comprises at least repeat units derived from VDF, repeat units derived from at least one PAE.

[0016] In some embodiments, the VDF-PAE copolymers of the present disclosure provide the desired repellency while having low levels of C7 to C20 PFCAs (e.g., less than 200 ppb). In some embodiments, the copolymers have a glass transition temperature (Tg) of no greater than

20 °C, no greater than 10, or even no greater than 0 °C.

[0017] In the fluoropolymers of the present disclosure, one or more PAEs are copolymerized with VDF. In some embodiments, the copolymers consist of a copolymer of VDF and one or more PAEs. In some embodiments, optionally, the copolymer may also include repeat units derived from other comonomers.

[0018] Generally, the perfluoro(allyl ethers) are described by Formula 1:

CF ₂ =CF-CF ₂ -0-(CF ₂ ) _m -0 _p -(CF ₂ ) _n -F (1) wherein: m = 1 to 6, p is 0 or 1, and n = 0 to 6, provided that when p is 1, n is not 0.

[0019] In some embodiments, p and n are 0, resulting in PAEs described by:

CF ₂ =CF-CF ₂ -0-(CF ₂ ) _m -F (2)

As used herein, such perfluoro(alkyl allyl ethers) of Formula 2 are described as MA-m, where m is the number of carbon atoms in the alkyl group. For example MA-l is perfluoro(methyl allyl ether); i.e., CF ₂ =CF-CF ₂ -0-CF3, and MA-3 is perfluoro(propyl allyl ether), i.e., CF ₂ =CF-CF ₂ -0-CF ₂ - CF ₂ - CF3.

In some embodiments, m is 1 to 4, e.g., m is 3.

[0020] In some embodiments, p =1 and n is 1 to 6, resulting in PAEs described by:

CF ₂ =CF-CF ₂ -0-(CF ₂ ) _m -0-(CF ₂ ) _n -F (3) As used herein, such perfluoro(alkoxy alkyl allyl ethers) of Formula 3 are described as MA-mn, where m is the number of carbon atoms in the alkyl group and n is the number of carbon atoms in the alkoxy substituent. For example MA-31 is perfluoro(methoxy propyl allyl ether); i.e., CF2=CF-CF2-0-CF2-

CF2-CF2-O-CF3. In some embodiments, m is 1 to 4, e.g., m = 3. In some embodiments, n = 1 to 3, e.g., m= 1.

[0021] As used herein, the term“perfluoro(allyl ether)” and its abbreviation (PAE) that are represented by Formula 1, include both the perfluoro(alkyl allyl ethers) (“PAAE”) of Formula 2, and the perfluoro(alkoxy alkyl ethers) (“PAAAE”) of Formula 3.

[0022] In some embodiments, the fluoropolymers of the present disclosure contain at least 10 mole percent of one or more PAEs, wherein the mole percent is based on the total moles of all PAEs in the fluoropolymer compared to the total moles of all comonomers. In some embodiments, the

fluoropolymers comprise at least 15 mole%, at least 25 mole%, or even at least 35% percent PAEs. In some embodiments, the fluoropolymers comprise no greater than 45 mole%, e.g., no greater than 40 mole% PAEs. In some embodiments, the fluoropolymers comprise 10 to 45 mole percent, e.g., 15 to 30 mole percent of one or PAEs.

[0023] In some embodiments, the fluoropolymers of the present disclosure contain at least 20 weight percent of one or more PAEs, wherein the weight percent is based on the total weight of all PAEs in the fluoropolymer compared to the total weight of all comonomers. In some embodiments, the

fluoropolymers comprise at least 25 wt.%, at least 40 wt.%, or even at least 50 wt.% PAEs. In some embodiments, the fluoropolymers comprise no greater than 80 wt.%, e.g., no greater than 70 wt.%, or even no greater than 60 wt.% PAEs.

[0024] In the fluoropolymers of the present disclosure, the one or more PAEs are copolymerized with vinylidene fluoride. Generally, the fluoropolymers of the present disclosure contain at least 20 mole% VDF based on the total number of moles of all monomers in the fluoropolymer. In some embodiments, the fluoropolymers contain at least 25, e.g., at least 30 mole% VDF. In some embodiments, the fluoropolymers contain no greater than 90 mole%, no greater than 80, no greater than 70, or even no greater than 60 mole% VDF. In some embodiments, the fluoropolymer comprises 20 to 90 mole%, e.g., 30 to 50 mole%, of vinylidene fluoride based on the total moles of comonomers

[0025] In some embodiments, the glass transition temperature of the fluoropolymer is no greater than 20 °C, e.g., no greater than 10 °C, or even no greater than 0 °C. In some embodiments, such

fluoropolymers also have a low Mooney viscosity. For example, in some embodiments, the

fluoropolymer has a Mooney viscosity at 121 °C or no greaterthan 150, e.g., no greater than 100, or even no greater than 50. In some embodiments, the Mooney viscosity at 121 °C is 1 to 150, e.g., 1 to 100, or even 1 to 50.

[0026] In some embodiments, the fluoropolymers may be semi-crystalline. Generally, the melting point (Tm) is no greater than 150 °C, e.g., no greater than 100 °C, or even no greater than 50 °C. [0027] The fluoropolymers of the present disclosure may contain, optionally, units derived from further comonomers. Such comonomers may be fluorinated or non-fluorinated but preferably are fluorinated, chlorinated or chlorinated and fluorinated.

[0028] Generally, the optional comonomers contain an alphaolefmic functionality, i.e. a

CX _| X2=CX3- group wherein X _| . X2 and X3 are independently from each other F, Cl or H with the proviso that at least one is H or F. In some embodiments, each of X _j , X2 and X3 is F.

[0029] These optional comonomers may be functional comonomers, for example they may contain additional functional groups for example to introduce branching sites ("branching modifiers") or polar groups or end groups ("polarity modifiers"). Branching modifiers typically have a second alpha-olefmic group or are branched molecules themselves. Polarity modifiers include olefins having polar groups for example acid groups as additional functional groups.

[0030] The optional comonomers may include (i) other perfluorinated alpha-olefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP), (ii) F and Cl containing olefins such as chlorotrifluoroethylene, or (iii) non-fluorinated alpha olefins such as ethylene or propylene.

[0031] In some embodiments, the fluoropolymer comprises at least 10 mole% TFE, e.g., at least 20, or even at least 30 mole% TFE. In some embodiments, the fluoropolymer comprises no greater than 50 mole%, e.g., no greater than 40 mole% TFE.

[0032] In some embodiments, the fluoropolymer may include one or more perfluoro(alkyl vinyl ethers) (PAVE) comonomers, e.g., at least 1 mole%, at least 2 mole %, or even at least 5 mole% PAVE. However, as longer-chain PAVEs may generate undesired perfluoroalkanoic acids, in some embodiments, the fluoropolymer may contain at least one of perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), or combinations thereof. In some embodiments, the fluoropolymer comprises PMVE. In addition, the amounts of such PAVEs may need to be limited; therefore, in some

embodiments, the fluoropolymers contain no greater than 30 mole%, e.g., no greater than 20 mole%, or even no greater than 10 mole% PAVEs. In some embodiments, the fluoropolymers are substantially free of PAVEs, i.e., the fluoropolymers contain less than 0.5 mole%, e.g., no greater than 0.1., or even no greater than 0.01 mole%.

[0033] In prior art crosslinked formulations, curesite groups such as bromo-groups, an iodo-groups, or cyano-groups were introduced by the addition curesite monomers (CSM) or chain transfer agents. In contrast, the fluoropolymers of the present disclosure do not include a curesite-group. However, as a result of typical raw material supply and manufacturing conditions, such curesite groups may be present in trace amounts, e.g., no greater than 5 parts per million (ppm) by weight based on the total weight of the fluoropolymer. In some embodiments, the fluoropolymer comprises no greater than 2 ppm, or even no greater than 1 ppm of curesite groups.

[0034] Even if no perfluorinated alkanoic acids are used in the production of fluoropolymers, e.g., if alternative fluorinated emulsifiers or no emulsifiers are being used, it has been found that perfluorinated alkanoic acids (in particular perfluorinated C6 to C12 acids) can be generated in the production of some copolymers. Perfluorinated alkanoic acids are represented by the formula F3C-(CF2)y-COOM; wherein y is an integer of 4 to 18. M is H in case of the free acid or a cation in case the acid is present as a salt. In case of perfluorooctanoic acid, y is 6 to give a total amount of carbon atoms of 8 (“C8-acid”).

[0035] Generally, the amount of perfluorinated alkanoic acids can be determined by extraction. The extraction of the perfluorinated alkanoic acids is typically done by treating a solid, finely dispersed/milled polymer sample with methanol (at 50 °C for 16 hours) separating the polymer from the liquid phase and determining the amount of acid in the separated (extracted) liquid phase.

[0036] In some embodiments the fluoropolymers according to the present disclosure are essentially free of perfluorinated alkanoic acids, in particular such acids with 6 to 20 carbon atoms.“Essentially free” in this context refers to amounts of less than 1 ppm, less 500 ppb, less than 200 ppb, less than 100 ppb, or even less than 50 ppb (based on the weight of polymer).

[0037] Provided that no perfluorinated alkanoic acids are used in the production of fluoropolymers, as polymerized, in some embodiments the fluoropolymers according to the present disclosure are essentially free of perfluorinated alkanoic acids, in particular such acids with 6 to 20 carbon atoms, i.e., less than 1 ppm, less 500 ppb, less than 200 ppb, less than 100 ppb, or even less than 50 ppb (based on the weight of polymer).“As polymerized” in this context means the polymerized product prior to any post-processing steps known to be useful for removing perfluorinated alkanoic acids, e.g., anion exchange.

[0038] Preferably, the polymers contain extractable perfluorooctanoic acid in an amount of less than 50 ppb and preferably less than 20 ppb (based on the weight of the polymer), for example from 2 to 20 ppb (based on the weight of the polymer).

[0039] Generally, known methods may be used to prepare the fluoropolymers of the present disclosure. In some embodiments, the copolymers described herein may be prepared by emulsion or suspension polymerization in an aqueous phase. In case of emulsion polymerization an emulsifier is used. In case of a suspension polymerization no emulsifier is used. In some embodiments emulsion polymerization is preferred as it results in stable dispersions.

[0040] Generally, the PAEs and VDF are copolymerized in the presence of initiators and optional additional comonomers described above. The various monomers are used in effective amounts to produce a copolymer with the properties described herein. Effective amounts are within the amounts described and exemplified herein.

[0041] If fluorinated emulsifiers are employed in the aqueous emulsion polymerization, the polymerization is carried out without adding any perfluorinated alkanoic acid, and in particular the polymerization is carried out without adding perfluorinated octanoic acid. Alternative fluorinated emulsifiers or non-fhiorinated emulsifiers may be used instead. When used, a fluorinated alternative emulsifier is typically used in an amount of 0.01 % by weight to 1 % by weight based on solids (polymer content) to be achieved. Suitable alternative fluorinated emulsifiers include those that correspond to the general formula: [R _j 0-L-C00 ] _j X _j wherein L represents a linear or branched or cyclic partially or fully fluorinated alkylene group or an aliphatic hydrocarbon group, Rf represents a linear or branched, partially or fully fluorinated aliphatic group or a linear or branched partially or fully fluorinated group interrupted once or more than once by an ether oxygen atom, X _j ⁺ represents a cation having the valence I, and i is 1, 2 or 3. In case the emulsifier contains partially fluorinated aliphatic groups it is referred to as a partially fluorinated emulsifier.

Preferably, the molecular weight of the emulsifier is less than 1,500 g/mole. Specific examples are described in, for example, U.S. Pat. Publ. 2007/0015937 (Hintzer et al.).

[0042] The aqueous emulsion polymerization may be initiated with a free radical initiator or a redox- type initiator. Any of the known or suitable initiators for initiating an aqueous emulsion polymerization can be used. Suitable initiators include organic as well as inorganic initiators. The amount of the polymerization initiator may suitably be selected, but it is usually from 2 to 600 ppm, based on the mass of water used in the polymerization.

[0043] The polymerization is preferably carried out by polymerizing the comonomers simultaneously. Typically, the reaction vessel is charged with the ingredients and the reaction is started by activating the initiator. In one embodiment the comonomers are then continuously fed into the reaction vessel after the reaction has started. They may be fed continuously at a constant comonomer ratio or at varying comonomer ratio.

[0044] The aqueous emulsion polymerization, whether done with or without seed particles, will preferably be conducted at a temperature of at least 65 °C, preferably at least 70 °C. Lower temperatures may not allow to introduce sufficient amounts of PAE into the polymer to reach the required comonomer content. Upper temperatures may typically include temperatures of 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, or even 150 °C.

[0045] The polymerization will preferably be conducted at a pressure of at least 0.5, 1.0, 1.5, 1.75,

2.0, or even 2.5 MPa (megaPascals); at most 2.25, 2.5, 3.0, 3.5, 3.75, 4.0, or even 4.5 MPa.

[0046] In some embodiments, the aqueous emulsion polymerization is carried out until the concentration of the polymer particles in the aqueous emulsion is at least 5, 10, or even 15 % by weight (also referred to as“solid content”).

[0047] In the resulting dispersion, the average particle size of the polymer particles (i.e., primary particles) is at least 50, 100, or even 150 nm; at most 250, 275, 300, or even 350 nm (D50). The particle sizes of dispersions can be determined by inelastic light scattering.

[0048] After the conclusion of the polymerization reaction, the dispersions may be treated by anion exchange to remove the alternative fluorinated emulsifiers if desired. Methods of removing the emulsifiers from the dispersions by anion-exchange and addition of non-ionic emulsifiers are disclosed for example in EP 1 155 055 B 1, by addition of polyelectrolytes are disclosed in WO2007/142888 or by addition of non-ionic stabilizers such as polyvinyl alcohols, polyvinyl esters and the like. [0049] The fluoropolymer content in the dispersions may be increased by up-concentration, for example using ultrafiltration as described, for example in US 4,369,266 or by thermal decantation (as described for example in US 3,037,953) or by electrodecantation. The solid content of up-concentrated dispersions is typically about 30 to about 70 % by weight.

[0050] The dispersions may further contain ingredients that may be beneficial when coating or impregnating the dispersion on a substrate, such as adhesion promoters, friction reducing agents, pigments and the like. Optional components include, for example, buffering agents and oxidizing agents as may be required or desired for the various applications.

[0051] In some embodiments of the present disclosure, the copolymers are provided in the form of a coating comprising the copolymer dissolved or dispersed in a solvent. For example, in some

embodiments, an aqueous dispersion of the copolymer may be used as a coating.

[0052] In some embodiments, such aqueous dispersions can include conventional cationic, nonionic, anionic, and/or zwitterionic (i.e., amphoteric) surfactants (i.e., emulsifiers). A mixture of surfactants may be used, e.g., containing nonionic and ionic surfactants. Suitable nonionic surfactants can have high or low HUB values, such as those available under the trade name TERGITOU from Dow DuPont, and the like. Suitable cationic surfactants include mono- or bi-tail ammonium salts. Suitable anionic surfactants include sulfonic and carboxylic aliphatic compounds and their salts, such as sodium dodecylbenzene sulphonate (available from Rhodia, France), and the like. Suitable amphoteric surfactants include cocobetaines, sulphobetaines, amine-oxides, and the like. In certain embodiments, surfactants suitable for use in the treating compositions of the present disclosure are described in International Publication No. WO 2013/162704 (Coppens et ak).

[0053] In some embodiments, the copolymers may be dissolved in a solvent, for example a solvent comprising a fluorinated organic solvent to form a coating. As used herein, "fluorinated organic solvent" is used as generally accepted in the art of organofluorine chemistry, and includes, but is not restricted to, fluorinated organic compounds generally taking the form of a carbon backbone substituted with fluorine atoms and optionally substituted with hydrogen and/or chlorine or other halogen atoms. The carbon backbone can be interrupted by heteroatoms such as divalent oxygen, trivalent nitrogen, sulfur, etc. Examples of fluorinated solvents include hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), hydrofluoroethers (HFEs), hydrohalofluoroethers (HEFEs) such as hydrochlorofluoroethers (HCFEs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), chlorofluorocarbons (CFCs), fluoroketones, perfluoroketones, and hydrochlorofluorocarbons (HCFCs), alone or as a mixture.

[0054] In some embodiments, the coatings may be used, for example, to laminate, coat and/or infuse into a substrate to form an article. The substrate or the treated surface thereof may be an inorganic or organic material. The substrate may be, for example a fiber, a fabric, a granule or a layer. Typical substrates include organic or inorganic fibers, preferably glass fibers, organic or inorganic fabrics, granules (such as polymer beads) and layers containing one or more organic polymers, including, for example, fluoropolymers. The fabrics may be woven or non-woven fabrics. The substrate may also be a metal or an article containing a metal surface or a fluoropolymer surface or layer, such as but not limited to PTFE surface or layers.

[0055] In some embodiments, the fluoropolymers may also be processed as solids. To provide the fluoropolymers in dry form, it must be separated from the dispersion. The fluoropolymers described herein may be collected by deliberately coagulating them from the aqueous dispersions by methods known in the art. In one embodiment, the aqueous emulsion is stirred at high shear rates to deliberately coagulate the polymers. Other salt-free methods include the addition of mineral acids. If salt content is not a problem, salts can be added as coagulating agents, such as for example, chloride salts (e.g., MgC^) or ammonium carbonate. Agglomerating agents such as hydrocarbons like toluenes, xylenes and the like may be added to increase the particle sizes and to form agglomerates. Agglomeration may lead to particles (secondary particles) having sizes of from about 0.5 to 1.5 mm.

[0056] Drying of the coagulated and/or agglomerated polymer particles can be carried out at temperatures of, for example, from 100 °C to 300 °C. Particle sizes of coagulated particles can be determined by electron microscopy. The average particle sizes can be expressed as number average by standard particle size determination software. The particle sizes may be further increased by melt pelletizing. The particles may have a particle size (longest diameter) of from at least 2, typically from about 2 to about 10 mm.

[0057] Advantages and embodiments of this invention are further illustrated by way of examples. However, the examples are not meant to limit the disclosure to the examples provided. The disclosure can be practiced with other materials, ranges and embodiment within the scope of the claims.

[0058] Examples

[0059] In case the methods description refers to standards like DIN, ASTM, ISO etc. and in case the year the standard was issued is not indicated, the version that was in force in 2018 is meant. In case no version was in force in 2018 anymore, for example because the standard has not been renewed or has expired, the version in force at the date closest to 2018 is to be used.

[0060] Tm Method. Melting peaks of the fluoropolymers were determined according to ASTM 4591 by means of Perkin-Elmer DSC 7.0 under nitrogen flow and a heating rate of l0°C/min. The indicated melting temperature (Tm) refers to the melting peak maximum.

[0061] Tg Method. Glass transition temperatures of the fluoropolymers were determined according to ASTM E1356 by means of Perkin-Elmer DSC 7.0 under nitrogen flow and a heating rate of 10 degrees C/min. The indicated glass transition temperature (Tg) refers to the midpoint temperature as defined in the test method.

[0062] Mooney Viscosity Method. Mooney Viscosities of the fluoropolymers were determined according to ASTM D1646 by means of an Alpha Technologies Mooney MV 2000 rheometer, with a measurement temperature of 121 °C, a pre-conditioning time of 1 minute, and a testing time of 10 minutes, using the large rotor - ML 1 + 10 at 121 °C. [0063] Comonomer Content Method. The comonomer content of the polymer was determined by solid state NMR. Samples were packed into a 3.2 mm rotor with a small amount of 2,2-bis(4- methylphenyl) hexafluoropropane as cross-integration standard. Diatomaceous earth was used instead of the fluoropolymer spacers in the rotor. Spectra were collected on a Varian 400 MHz NMRS solid state NMR spectrometer equipped with a 3.2 mm Varian HFXY MAS probe at 18 kHz MAS at 180 °C. The

1H spectra were collected before and after the spectra.

[0064] Alternatively, the comonomer content in the polymers described can be determined by infrared spectroscopy using a Thermo Nicolet Nexus FT-IR spectrometer. HFP comonomer content - if present- can be determined as described in US 4,675,380. Alternatively, the composition can be determined for certain polymers by dissolving them in e.g., acetone, and measure the composition according to literature (Macromolecules 2002, 35, 8694ff).

[0065] Solid Content Method. The solid content (fluoropolymer content) of the dispersions can be determined gravimetrically according to ISO 12086. A correction for non-volatile inorganic salts is not carried out. The solid content of the polymer dispersions is taken as polymer content.

[0066] Particle Size Method. The latex particle size determination can be conducted by means of dynamic light scattering with a MALVERN ZETASIZER 1000 HSA in accordance to ISO/DIS 13321. The particle size is determined as volume -average and expressed as D50. Prior to the measurements, the polymer latexes as yielded from the polymerizations are diluted with 0.001 mol/L KCl-solution. The measurement temperature was 20 °C in all cases.

[0067] MA-3: CF2=CF-CF2-0-CF2-CF2-CF3 was purchased from Anles, St. Petersburg, Russia.

[0068] Example 1. A 50 L-polymerization kettle was charged with 29 L of ¾(), 300 g of a 30 wt. of a fluorinated emulsifier (CF3-0-[CF2]3-0CFHCF2-C00NH4, see US 7,671,112) and stirred at an agitator speed of 240 rpm. The kettle was heated up to 90 °C and purged with nitrogen. Then the following monomers were charged: VDF until 1.0 bar was reached, MA-3 until pressure increased from 1.0 to 2.9 bar and again VDF until pressure increased to 6.0 bar. The polymerization was initiated by adding 4.0 g of ammonium persulfate (APS). Over 303 min, 3.70 kg of VDF (76 mole%), 5.77 kg of MA- 3 (24 mole%), and 1960 g of a 2 wt.% solution of APS was fed continuously to maintain the pressure.

The reaction was stopped. The resulting polymer dispersion had a solid content of 22 wt.%. The average particle size of the polymer in the dispersion was 97 nm.

[0069] The polymer was isolated by coagulation with MgCl2. A Tg of -29 °C and a Mooney viscosity ML 1+10 of 35 was found. The incorporation of MA-3 was determined from 19 F-NMR by comparing the integrals of the -O-CF2CF2CF3 signals from the MA-3 at -129 ppm to the -CF2- signals from VDF as described in the literature (Macromolecules 2002, 35, 8694-8707). A composition of 25 mole% of MA-3 and 75 mole% of VDF was found.

[0070] Example 2. A 50 L-polymerization kettle was charged with 29 L of ¾(), 300 g of a 30 wt. of the fluorinated emulsifier of Example 1 and stirred at an agitator speed of 240 rpm. The kettle was heated up to 90 °C and purged with nitrogen. Then the following monomers were charged: VDF until 1.0 bar was reached, MA-3 until pressure increased from 1.0 to 2.9 bar and again VDF until pressure increased to 6.0 bar. The polymerization was initiated by adding 8.0 g of APS. Over 319 minutes, 4.00 kg of VDF (84 mole%), 3.80 kg of MA-3 (16 mole%), and 1960 g of a 2 wt.% solution of APS was fed continuously to maintain the pressure. The reaction was stopped. The resulting polymer dispersion had a solid content of 24 wt.%. The average particle size of the polymer in the dispersion was 82 nm. The polymer was isolated by coagulation with MgQ2. A Tg of -31 °C, a Tm of 83 °C, and a Mooney viscosity MU 1+10 of 32 were measured.

[0071] Example 3. A 50 U-polymerization kettle was charged with 29 U of F^O, 300 g of a 30 wt.% of the fluorinated emulsifier of Example 1 and stirred at an agitator speed of 240 rpm. The kettle was heated up to 90 °C and purged with nitrogen. Then the following monomers were charged: VDF until 1.0 bar was reached, MA-3 until pressure increased from 1.0 to 2.0 bar, PMVE from 2.0 to 3.8 bar and again VDF until pressure increased to 6.0 bar. The polymerization was initiated by adding 8.0 g of APS. Over 146 min, 1.65 kg of VDF (70 mole%), 1.17 kg of MA-3 (20 mole%), 1.23 kg of PMVE (10 mole%) and 1960 g of a 2 wt.% solution of APS was fed continuously to maintain the pressure. The reaction was stopped. The resulting polymer dispersion had a solid content of 11 wt.%. The average particle size of the polymer in the dispersion was 90 nm. The polymer was isolated by coagulation with MgC^. A Tg of -28 °C and a Mooney viscosity ML 1+10 of 65 were measured.

[0072] Treatment Procedure via“Padding” Process. The fluoropolymer was applied onto the fabric substrates by immersing the substrates in the treatment dispersion and agitating until the substrate was saturated. The saturated substrate was then run through a padder/roller to remove excess of the dispersion and to obtain a certain % Wet Pick Up (WPU), wherein:

WPU = 100

[0073] For example, a WPU of 100 means that after this process the substrate absorbed 100% of its own weight of the treatment dispersion before drying). Samples were then dried and cured at 170 °C for 3 minutes.

[0074] Solids on Fabric (“SOF”). SOF is calculated based on the weight fraction of the dispersion in the formulation (A), the weight fraction of the solids of the formulation (S), and the measured wet pick up (WPU) according to the following formula:

SOF(%) = (A x S x WPU).

For example, if the fabric is treated with a formulation containing 6.7 wt.% of the fluoropolymer dispersion having a solids content of 30 wt.%, then at 50 WPU, the % SOF will be: 0.067 x 0.30 x 50 = 1% Solids on Fabric. [0075] Spray Rating Method. The spray rating (SR) of a treated substrate is a value indicative of the dynamic repellency of the treated substrate to water that impinges on the treated substrate. The repellency was measured by Test Method 22-1996, published in the 2001 Technical Manual of the American Association of Textile Chemists and Colorists (AATCC), and is expressed in terms of a‘spray rating’ of the tested substrate. The spray rating was obtained by spraying 250 milliliters water on the substrate from a height of 15 centimeters. The wetting pattern was visually rated using a 0 to 100 scale, where 0 means complete wetting and 100 means no wetting at all. Spray rating was measured initially and after the fabric was laundered 5 or 20 times (designated as 5L or 20L respectively).

[0076] The laundering procedure consisted of placing a 400 - 900 square centimeter sheet of treated substrate in a washing machine (A Kenmore Elite washing machine) along with ballast sample (1.9 kilograms (kg) of 8-ounce fabric). A commercial detergent (“TIDE” available from Proctor & Gamble)

38 grams (g)) was added. The substrate and ballast load were washed using a short wash cycle at 40 °C, followed by a rinse cycle and centrifuging. The sample was not dried between repeat cycles. After the required cycles, the textile samples were dried in a Miele T-356 tumble drier, at a setting of“high”.

[0077] Oil Repellency Method. The oil repellency (OR) of a treated substrate is measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No 118-1983, which is based on the resistance of a treated substrate to penetration by oils of varying surface tensions (see U.S. Patent No. 5,910,557). Ratings from 1 to 8 were assigned, with higher values indicating better oil repellency.

[0078] Water Repellency (WR) Method. The water repellency (WR) of a substrate was measured using a series of water-isopropyl alcohol test liquids and was expressed in terms of the "WR" rating of the treated substrate. The WR rating corresponded to the most penetrating test liquid which did not penetrate or wet the substrate surface after 15 seconds exposure. Substrates which were penetrated by or were resistant only to 100% water (0% isopropyl alcohol), the least penetrating test liquid, were given a rating of 0, whereas substrates resistant to a test liquid of 100% isopropyl alcohol (0% water), the most penetrating test liquid, were given a rating of 10. Other intermediate ratings were calculated by dividing the percent isopropyl alcohol in the test liquid by 10, e.g., a treated substrate resistant to a 70%/30% isopropyl alcohol/water blend, but not to an 80%/20% blend, would be given a rating of 7.

[0079] Performance Testing on Fabric.

[0080] Fabric A: Taslan Dobby woven nylon fabric (NTD), having a basis weight of 115 grams per square meter. The nylon fabric is characterized by the Chinese manufacturer as 70D* l60D/l66T*83T, dyed and prepared for finishing.

[0081] Fabric B: Poly Pongee woven polyester fabric (PPP), having a basis weight of 84 grams per square meter. The polyester fabric is characterized by the Chinese manufacturer as 75D*75D/l45T*90T, dyed and prepared for finishing. [0082] Samples were prepared with Fabrics A and B according to the Treatment Procedure via

“Padding” Process using the fluoropolymer composition of Example 3. The results are summarized in Table 1.

Table 1: Test Results using the fluoropolymer of Example 3.

[0083] Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.