Dispersible ionomer powder and method for making the same

Abstract

The present invention relates to certain dispersible ionomer powders made from particles contained in quasi-spherical hollow agglomerates of primary particles, a process for the manufacture of these dispersible ionomer powders involving spray drying a latex of the ionomers, and methods of using these dispersible ionomer powders, especially for coating applications.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority from European application No. 18204459.4, filed on November 5, 2018, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] The present invention relates to certain dispersible ionomer powders, methods for their manufacture, and methods of their use, particularly for coating applications. Background Art

[0004] Fluorinated ionomers having carboxylic or sulfonic acid groups, and more specifically perfluorosulfonic acid (PFSA) polymers, are semi-crystalline materials that are known to be difficult to dissolve / disperse in solvents except using harsh conditions (ie, 250° C. in water under pressure).

[0005] In practice, the raw polymerized material is usually provided in the form of a latex of polymer precursors which needs to undergo hydrolysis to achieve ion exchange capacity. Once coagulated and hydrolyzed, the acid form material can be redispersed in water (possibly mixed with a small amount of alcohol solvent) simply by extensive heat treatment to provide dispersed particles in the aqueous phase.

[0006] Currently, end users may need to formulate the acid form material into coating compositions based on solvents other than water, for example for impregnation of various supports, so that the availability of readily dispersible powders of the fluorinated ionomers would be very beneficial in this market space.

[0007] Therefore, in this field, document US 2008 / 0227875 discloses solid and liquid compositions comprising particles of a highly fluorinated ion exchange polymer having sulfonate functional groups. The liquid aqueous composition is produced by dispersing the polymer in an aqueous medium under strict conditions of high temperature and high agitation. The liquid component of the aqueous liquid composition can be removed by evaporation at a temperature below the coalescence temperature of the ion exchange polymer in the composition to produce a solid composition from the liquid composition. "Coalescence temperature" means the temperature at which the dry solid of the polymer solidifies into a stable solid that is not redispersible in water or other polar solvents under mild conditions (i.e., room temperature / atmospheric pressure). This document teaches that the coalescence temperature varies with the polymer composition, with preferred conditions being those in which the liquid component is removed by heating to a temperature of less than about 100°C. Among the techniques used to achieve this removal, freeze drying and spray drying at a temperature less than the coalescence temperature are mentioned. The result of this method is a redispersible powdered composition of a fluoroionomer.

[0008] Similarly, document US 2008 / 0160351 relates to a method for preparing a dispersion of a highly fluorinated ion exchange polymer, comprising the steps of atomizing a dispersion of the polymer in an organic liquid in a heated gas and redispersing the particles thus obtained in a second liquid. In this example, a fluoroionomer dispersion is first prepared under relatively harsh conditions in a liquid medium comprising an alcohol (NPA) aqueous solution in an amount of about 20% to 25%. The alcohol / water dispersion is then spray-dried in a nitrogen stream maintained at a temperature of 170° C. to 210° C., thereby producing particles having a residual moisture content of about 4% to 5% by weight, a particle size of about 25 μm to 40 μm, and a bulk density of 30 g / l to 50 g / l. The powder thus obtained is readily redispersed in liquid media of varying compositions at room temperature.

[0009] Still, document CN 103044698 B relates to a method for making a membrane, wherein a perfluorinated sulfonic acid resin is dissolved in a low-boiling point solvent to obtain a solution with a low solid content of 3 wt.% to 15 wt.%; in a second step, the solution is filtered and spray-dried to provide a perfluorinated sulfonic acid resin powder; and in a subsequent step, the powder thus obtained is redissolved in a high-boiling point solvent to prepare a solution with a high solid content of 25 wt.% to 50 wt.%; and bubbles on the solution are removed and the solution is coated on a solid surface to form a film, dried and rolled to obtain a perfluorinated sulfonic acid ion exchange membrane.

[0010] Furthermore, document US 2011 / 0240559 describes a method for purifying a liquid PFSA dispersion by contacting it with solid particles of a PFSA having SO3H groups; this solid particulate PFSA having acid groups is obtained from a perfluorosulfonic acid precursor having sulfonyl fluoride groups prepared by emulsion polymerization, and is further coagulated, hydrolyzed, and dried. This document does not describe the hydrolysis of the PFSA precursor in latex form, nor does it describe spray drying techniques.

[0011] Now, although the problem of providing redispersible fluorinated ionomer powders has been solved in the prior art, the handling of the resulting dispersions for formulating coating compositions remains a challenge, since the achievable concentrations are still relatively low and the corresponding viscosities in the liquid state are often too low to be compatible with standard coating liquid formulating techniques, making it necessary to correct the viscosity of the resulting formulation by adding viscosity modifiers and / or thickeners, which may then remain residual in the final coated / impregnated article.

[0012] Thus, there remains a need in the art for methods of providing dispersible fluoroionomer powders, and fluoroionomer powders provided by these methods, which can address unmet market needs including the delivery of high solids, high viscosity formulations in a variety of solvents via simple manufacturing methods. Summary of the Invention

[0013] Faced with this technical problem, the Applicant has discovered a method for making ionomer powders which is particularly advantageous in that it avoids the use of harsh conditions and delivers particles having particularly advantageous properties, in particular with regard to the liquid viscosities of the formulations thus achievable.

[0014] Thus, in a first aspect, the present invention relates to a method for producing a powdered material [material (P)] consisting of a plurality of particles of at least one ionizable polymer comprising a plurality of ionizable groups selected from the group consisting of -SO3X a 、-PO3X a and-COOX a A group consisting of X a is H, an ammonium group or a metal, preferably a monovalent metal [ionomer (I X )], the method comprising:

[0015] Step (1): providing an aqueous latex of raw polymer [latex (Ip)], the latex (Ip) comprising particles of at least one ionomer precursor comprising a plurality of hydrolyzable groups selected from the group consisting of -SO2X X 、-PO 2X and-COX x A group consisting of X x is a halogen, specifically F or Cl [precursor (I P )];as well as

[0016] Step (2): In order to make the group -SO2X X 、-PO2X X and-COX x At least partially converted into the corresponding group -SO3X a 、-PO3X a and-COOX a Without causing any significant coagulation, the original polymerized aqueous latex [latex (I x )] is contacted with an alkaline hydrolyzing agent [reagent (B)] to obtain an ionomer (I X ) of an aqueous latex of particles, wherein X x is F or Cl, where X a is H, ammonium or monovalent metal;

[0017] Optionally, step (3): making the latex (I x ) is contacted with at least one ion exchange resin to at least partially remove reagent (B) residues and / or other contaminants; and

[0018] Step (4): After purification, the latex (I x ) is spray-dried to obtain said material (P).

[0019] In a second aspect, the present invention relates to a powdery material [material (P)] obtainable by the process as described above, said powdery material consisting of a plurality of particles of at least one fluorinated ionomer comprising a plurality of ionizable groups selected from the group consisting of -SO3X a 、-PO3X a and-COOX a A group consisting of X a is H, an ammonium group or a metal, preferably a monovalent metal [ionomer (I X )],

[0020] The particles are present in quasi-spherical hollow agglomerates of elementary particles;

[0021] - the average particle size of the hollow agglomerates is from 1 μm to 150 μm; and

[0022] - The average diameter of the primary particles is between 15 nm and 150 nm.

[0023] In particular, the applicant has found that the process of the present invention (which does not involve any steps of coagulating and then re-dissolving the precursor / ionomer) is particularly efficient from an economic point of view and uses relatively mild conditions for processing the precursor into a powdered material, and is therefore very advantageous in itself. Furthermore, the process as detailed above provides a powdered material with a particularly advantageous particle microstructure that allows it to be easily redissolved and provides increased liquid viscosity so that formulations made therefrom can match the viscosity requirements of a large number of coating / liquid processing technologies without the need for the addition of artificial viscosity enhancers and / or thickeners.

[0024] Ionizable polymers [ionomers (I X )] and ionomer precursor [precursor (I P )]

[0025] Ionizable polymers (also referred to as ionomers of the present invention) X ) and its precursor (I P )) is typically fluorinated, that is, comprises repeating units derived from an ethylenically unsaturated monomer comprising at least one fluorine atom, and may further comprise repeating units derived from at least one hydrogenated monomer, wherein the term "hydrogenated monomer" is intended to mean an ethylenically unsaturated monomer comprising at least one hydrogen atom but no fluorine atoms.

[0026] As mentioned, ionomer (I X ) including those selected from -SO3X a 、-PO3X a and-COOX a A plurality of ionizable groups consisting of a group wherein X a is H, an ammonium group or a metal, preferably a monovalent metal, and the precursor (I p ) including those selected from -SO2X X 、-PO2X X and-COX x A plurality of hydrolyzable groups consisting of x is a halogen, specifically F or Cl [precursor (I P )].

[0027] As in ionomer (I X ) is suitable as a counterion X in the ionizable group a Examples of preferred monovalent metals include Li, K, Na, among which for the ionomer (I X ) in certain areas of use (e.g., in combination with its + / Li redox couple in the field of secondary batteries and other electrochemical devices), Li may be preferred.

[0028] Typically, ionomers (I X ) comprises the ionizable group as a pendant group covalently bonded to a hydrolyzable repeat unit derived from a functional monomer (hereinafter monomer (X)). Similarly, the precursor (I P ) typically comprises the hydrolyzable group as a pendant group covalently bonded to a repeating unit derived from the functional monomer (hereinafter monomer (X)).

[0029] The expression "derived from a hydrolyzed repeating unit" in conjunction with a specific monomer is intended to indicate that the repeating unit is first derived / obtained directly from polymerizing said specific monomer and then derived / obtained by further modifying / finishing said specific monomer by hydrolysis.

[0030] Ionomer (I X ) may consist essentially of a sequence of hydrolyzed repeating units derived from one or more than one monomer (X) as described above in detail, or may be a copolymer comprising hydrolyzed repeating units derived from one or more than one monomer (X) and repeating units derived from one or more than one additional monomer different from monomer (X). Similarly, ionomers (I X )'s precursor (I P) may consist essentially of a sequence of repeating units derived from one or more than one monomer (X) as described above in detail, or may be a copolymer comprising repeating units derived from one or more than one monomer (X) and repeating units derived from one or more than one further monomer different from monomer (X).

[0031] Typically, monomer (X) is a fluorinated monomer; further, one or more additional monomers different from monomer (X) may be fluorinated monomers. The expression "fluorinated monomer" is intended to encompass ethylenically unsaturated monomers comprising at least one fluorine atom.

[0032] According to certain embodiments of the present invention, the ionomer (I X ) includes multiple -SO3X as detailed above a Group, that is, ionomer (I SO3X According to these embodiments, the precursor (I P ) includes multiple groups as detailed above -SO2X X , that is, the precursor (P SO2X ).

[0033] Ionomer (I SO3X ) can be essentially derived from one or more than one of the above-described compounds including compounds having the formula -SO3X a A monomer (X SO3X ) or may comprise a sequence of multiple repeating units derived from one or more than one monomer (X SO3X ) and multiple repeating units derived from one or more than one monomer different from (X SO3X ) is a repeating unit of another monomer.

[0034] Similarly, the precursor (P SO2X ) can be essentially derived from one or more than one of the above-described compounds including compounds having the formula -SO2X X A monomer (X P SO2X ) or may comprise a sequence of multiple repeating units derived from one or more than one monomer (X P SO2X ) and multiple repeating units derived from one or more than one monomer different from (X P SO2X ) is a repeating unit of another monomer.

[0035] Including multiple-SO3X a Suitable preferred ionomers (I SO3X ) are those polymers consisting essentially of: a plurality of hydrolyzed repeating units comprising at least one -SO3Xa Group, where X a is H, an ammonium group or a metal, preferably a monovalent metal; and is derived from a compound comprising at least one -SO2X X at least one ethylenically unsaturated fluorinated monomer of the group, wherein X x is halogen [hereinafter referred to as monomer (A)]; and a plurality of repeating units derived from at least one of the above-described monomers containing no -SO2X X The corresponding precursor (P SO2X ) are those polymers consisting essentially of: as detailed above including at least one -SO2X X groups and derived from a plurality of repeating units of at least one ethylenically unsaturated fluorinated monomer comprising at least one monomer (A); and a plurality of repeating units derived from at least one monomer (B) as described in detail above.

[0036] As mentioned above, the expression "derived from the hydrolysis repeating unit of..." in conjunction with the specific monomer (A) is intended to indicate that the repeating unit is first derived / directly obtained from polymerizing said specific monomer and then further modified / elaborated by further modifying / elaborating said specific monomer (by hydrolysis, X Group (wherein X X is halogen) is converted into at least one -SO3X a Group (wherein X a is H, an ammonium group or a metal, preferably a monovalent metal).

[0037] With reference to both types of monomers (A) and (B), the phrase "at least one monomer" is used herein to indicate that one or more than one monomer of each type may be present in the ionomer (I SO3X ) and / or precursors (P SO2X Hereinafter, the term monomer will be used to refer to both one and more than one monomer of a given type.

[0038] Non-limiting examples of suitable monomers (A) are:

[0039] - sulfonyl halofluoroolefin having the formula: CF2=CF(CF2) p SO2X X , where X X is halogen, preferably F or Cl, more preferably F, wherein p is an integer between 0 and 10, preferably between 1 and 6, more preferably p is equal to 2 or 3;

[0040] -sulfonyl halide fluorovinyl ether having the formula: CF2=CF-O-(CF2) m SO2XX , where X X is halogen, preferably F or Cl, more preferably F, wherein m is an integer between 1 and 10, preferably between 1 and 6, more preferably between 2 and 4, even more preferably m is equal to 2;

[0041] - sulfonyl fluoride alkoxy vinyl ether having the formula: CF2=CF-(OCF2CF(R F1 )) w -O-CF2(CF(R F2 )) y SO2X X , where X X is halogen, preferably F or Cl, more preferably F; wherein w is an integer between 0 and 2, and R F1 and R F2 is independently F, Cl or C optionally substituted with one or more ether oxygens 1- C 10 Fluoroalkyl, y is an integer between 0 and 6; preferably, w is 1, R F1 is -CF3, y is 1 and R F2 It is F;

[0042] - having the formula CF2=CF-Ar-SO2X X Sulfonyl halide aromatic fluoroolefin, wherein X X is halogen, preferably F or Cl, more preferably F, wherein Ar is C5-C 15 Aromatic or heteroaromatic groups.

[0043] Preferably, monomer (A) is selected from the group consisting of monomers having the formula CF2=CF-O-(CF2) m The group of sulfonyl fluoride fluorovinyl ethers of -SO2F, wherein m is an integer between 1 and 6, preferably between 2 and 4.

[0044] More preferably, monomer (A) is CF2=CFOCF2CF2-SO2F (perfluoro-5-sulfonyl fluoride-3-oxa-1-pentene).

[0045] Non-limiting examples of suitable ethylenically unsaturated fluorinated monomers of type (B) are:

[0046] -C2-C8 perfluoroolefins, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and perfluoroisobutylene;

[0047] - C2-C8 hydrogen-containing fluoroolefins, such as trifluoroethylene (TrFE), vinylidene fluoride (VDF), vinyl fluoride (VF), pentafluoropropylene and hexafluoroisobutylene;

[0048] - C2-C8 chlorine- and / or bromine- and / or iodine-containing fluoroolefins, such as chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene;

[0049] - having the formula CF2=CFOR f1 Fluoroalkyl vinyl ether, wherein R f1 is a C1-C6 fluoroalkyl group, such as -CF3, -C2F5, -C3F7;

[0050] - a fluoroalkyl vinyl ether of the formula CF2=CFOX0, wherein X0 is a C1-C 12 Fluorooxyalkyl, these fluorooxyalkyl vinyl ethers include in particular those having the formula CF2=CFOCF2OR f2 Fluoromethoxyalkyl vinyl ether, wherein R f2 Is a C1-C3 fluoro(oxy)alkyl group, such as -CF2CF3, -CF2CF2-O-CF3 and -CF3

[0051] - Fluorodioxole having the formula:

[0052]

[0053] Among them, R f3 、R f4 、R f5 、R f6 Each of which is independently a fluorine atom, optionally a C1-C6 fluoro(halo)fluoroalkyl group including one or more oxygen atoms, such as -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3.

[0054] Preferably, monomer (B) is selected from the following:

[0055] - C2-C8 perfluoroolefins selected from tetrafluoroethylene (TFE) and / or hexafluoropropylene (HFP);

[0056] - a C2-C8 hydrogen-containing fluoroolefin selected from trifluoroethylene (TrFE), vinylidene fluoride (VDF) and vinyl fluoride (VF); and

[0057] - mixtures thereof.

[0058] According to these embodiments, preferably, the ionomer (I SO3X ) including multiple -SO3X a functional group and consists essentially of a sequence of a plurality of hydrolyzed repeating units derived from at least one ethylenically unsaturated fluorinated monomer (A) comprising at least one sulfonyl fluoride functional group (group -SO2F) and a plurality of repeating units derived from at least one ethylenically unsaturated fluorinated monomer (B). In these embodiments, the precursor (PSO2X ) consists essentially of a sequence of a plurality of repeating units derived from at least one ethylenically unsaturated fluorinated monomer (A) comprising at least one sulfonyl fluoride functional group (group -SO2F) and a plurality of repeating units derived from at least one ethylenically unsaturated fluorinated monomer (B).

[0059] In addition to the listed repeating units, a limited amount (less than 1 mol % relative to the total moles of repeating units) of end groups, impurities, defects and other spurious units may be present in the preferred ionomers (I SO3X ) and / or preferably precursor (P SO2X ) without substantially affecting the ionomer (I SO3X ) or precursor (P SO2X )’s nature.

[0060] According to certain embodiments, the ionomer (I SO3X ) or the corresponding precursor (P SO2X ) wherein at least one monomer (B) is TFE. Wherein said at least one monomer (B) is an ionomer (I) of TFE SO3X ) will hereby be referred to as ionomer (I TFE SO3X ), where the corresponding precursor (P SO2X ) will be referred to as the precursor (P TFE SO2X ).

[0061] Preferred ionomers (I TFE SO3X ) is selected from polymers consisting essentially of:

[0062] (1) Repeating units derived from tetrafluoroethylene (TFE), relative to ionomers (I TFE SO3X ), the amount of these repeating units (1) is generally 50 mol% to 99 mol%, preferably 52 mol% to 98 mol%;

[0063] (2) Includes at least one -SO3X a groups and derived from hydrolyzed repeating units of at least one monomer selected from the group consisting of:

[0064] (j) Sulfonyl halide fluorovinyl ether having the formula: CF2=CF-O-(CF2) m SO2X X , where X X is halogen, preferably F or Cl, more preferably F; wherein m is an integer between 1 and 10, preferably between 1 and 6, more preferably between 2 and 4, even more preferably, m is equal to 2;

[0065] (jj) Sulfonyl fluoride alkoxy vinyl ether having the formula: CF2=CF-(OCF2CF(R F1 )) w -O-CF2(CF(R F2 )) y SO2X X , where X X is halogen, preferably F or Cl, more preferably F; wherein w is an integer between 0 and 2, and R F1 and R F2 is independently F, Cl or C optionally substituted with one or more ether oxygens 1- C 10 Fluoroalkyl, y is an integer between 0 and 6; preferably, w is 1, R F1 is -CF3, y is 1 and R F2 is F; and (jjj) mixtures thereof;

[0066] Relative to ionomer (I TFE SO3X ), the amount of these repeating units (2) is generally 1 mol% to 50 mol%, preferably 2 mol% to 48 mol%; and

[0067] (3) optionally, repeating units derived from at least one hydrogenated and / or fluorinated monomer, preferably perfluorinated monomer, different from TFE, these monomers being generally selected from the group consisting of: hexafluoropropylene; having the formula CF2=CFOR' f1 Perfluoroalkyl vinyl ether, wherein R' f1 Is a C1-C6 perfluoroalkyl group, such as -CF3, -C2F5, -C3F7; having the formula CF2=CFOR' O1 Perfluoroalkyl vinyl ether, wherein R' O1 It is a C2-C 12 Perfluoroalkyl groups, such as perfluoroalkyl vinyl ethers, include, for example, those having the formula CF2=CFOCF2OR' f2 Perfluoroalkyl-methoxy-vinyl ether, wherein R' f2 Is C1-C6 perfluoroalkyl, such as -CF3, -C2F5, -C3F7; or C1-C6 perfluorooxyalkyl having one or more ether groups, such as -C2F5-O-CF3; relative to the ionomer (I TFE SO3X ), the amount of these repeating units (3) is usually 0 mol% to 45 mol%, preferably 0 mol% to 40 mol%.

[0068] Consistently, the preferred ionomers (I TFE SO3X ) of the preferred precursor (P TFE SO2X ) is selected from polymers consisting essentially of:

[0069] (1) Repeating units derived from tetrafluoroethylene (TFE), relative to the precursor (P TFE SO2X ), the amount of these repeating units (1) is generally 50 mol% to 99 mol%, preferably 52 mol% to 98 mol%;

[0070] (2) Repeating units derived from at least one monomer selected from the group consisting of:

[0071] (j) Sulfonyl halide fluorovinyl ether having the formula: CF2=CF-O-(CF2) m SO2X X , where X X is halogen, preferably F or Cl, more preferably F; wherein m is an integer between 1 and 10, preferably between 1 and 6, more preferably between 2 and 4, even more preferably, m is equal to 2;

[0072] (jj) Sulfonyl fluoride alkoxy vinyl ether having the formula: CF2=CF-(OCF2CF(R F1 )) w -O-CF2(CF(R F2 ))X X ,

[0073] where X X is halogen, preferably F or Cl, more preferably F; wherein w is an integer between 0 and 2, and R F1 and R F2 is independently F, Cl or C optionally substituted with one or more ether oxygens 1- C 10 Fluoroalkyl, y is an integer between 0 and 6; preferably, w is 1, R F1 is -CF3, y is 1 and R F2 is F; and

[0074] (jjj) mixtures thereof;

[0075] Relative to the precursor (P TFE SO2X ), the amount of these repeating units (2) is generally 1 mol% to 50 mol%, preferably 2 mol% to 48 mol%; and

[0076] (3) optionally, repeating units derived from at least one hydrogenated and / or fluorinated monomer, preferably perfluorinated monomer, different from TFE, these monomers being generally selected from the group consisting of: hexafluoropropylene; having the formula CF2=CFOR' f1 Perfluoroalkyl vinyl ether, wherein R' f1 Is a C1-C6 perfluoroalkyl group, such as -CF3, -C2F5, -C3F7; having the formula CF2=CFOR' O1 Perfluoroalkyl vinyl ether, wherein R' O1 It is a C2-C 12 Perfluoroalkyl groups, such as perfluoroalkyl vinyl ethers, include, for example, those having the formula CF2=CFOCF2OR' f2 Perfluoroalkyl-methoxy-vinyl ether, wherein R' f2 is a C1-C6 perfluoroalkyl group, such as -CF3, -C2F5, -C3F7; or a C1-C6 perfluorooxyalkyl group having one or more ether groups, such as -C2F5-O-CF3; relative to the precursor (P TFE SO2X ), the amount of these repeating units (3) is usually 0 mol% to 45 mol%, preferably 0 mol% to 40 mol%.

[0077] According to certain embodiments, the preferred ionomer (I TFE SO3X ) usually consists mainly of the following:

[0078] (k) from 55 mol % to 95 mol %, preferably from 65 mol % to 93 mol % of repeating units derived from TFE;

[0079] (kk) from 5 mol% to 45 mol%, preferably from 7 mol% to 35 mol% of at least one -SO3X as described in detail above a groups and are derived from the hydrolyzed repeating units of the monomer(s) (2);

[0080] (3) from 0 to 25 mol %, preferably from 0 to 20 mol %, of repeating units (3) derived from fluorinated monomer(s) different from TFE as detailed above,

[0081] The above items are as follows: TFE SO3X ) is based on the total moles of repeating units.

[0082] For the preferred precursor (P TFE SO2X), also mutatis mutandis, which comprises units (2) derived from monomer(s) as detailed above, rather than their corresponding hydrolyzed counterparts.

[0083] According to certain other embodiments, the ionomer (I SO3X ) or the corresponding precursor (P SO2X ) wherein at least one monomer (B) is VDF. Wherein at least one monomer (B) is an ionomer (I SO3X ) will hereby be referred to as ionomer (I VDF SO3X ), where the corresponding precursor (P SO2X ) will be referred to as the precursor (P VDF SO2X )

[0084] Preferred ionomers (I VDF SO3X ) is selected from polymers consisting essentially of:

[0085] (1) Repeating units derived from vinylidene fluoride (VDF), relative to ionomer (I VDF SO3X ) of the total moles of repeating units, the amount of these repeating units (1) is generally 55 mol% to 99 mol%, preferably 70 mol% to 95 mol%;

[0086] (2) Includes at least one -SO3X a groups and derived from hydrolyzed repeating units of at least one monomer selected from the group consisting of:

[0087] (j) Sulfonyl halide fluorovinyl ether having the formula: CF2=CF-O-(CF2) m SO2X X , where X X is halogen, preferably F or Cl, more preferably F, wherein m is an integer between 1 and 10, preferably between 1 and 6, more preferably between 2 and 4, even more preferably m is equal to 2;

[0088] (jj) Sulfonyl fluoride alkoxy vinyl ether having the formula: CF2=CF-(OCF2CF(R F1 )) w -O-CF2(CF(R F2 )) y SO2X X

[0089] where X X is halogen, preferably F or Cl, more preferably F, wherein w is an integer between 0 and 2, and R F1 and RF2 is independently F, Cl or C1-C1 optionally substituted with one or more ether oxygens 10 Fluoroalkyl, y is an integer between 0 and 6; preferably, w is 1, R F1 is -CF3, y is 1 and R F2 is F; and

[0090] (jjj) mixtures thereof;

[0091] Relative to ionomer (I VDF SO3X ), the amount of these repeating units (2) is generally 1 mol% to 45 mol%, preferably 5 mol% to 30 mol%; and

[0092] (3) optionally, repeating units derived from at least one hydrogenated monomer or fluorinated monomer different from VDF; relative to the ionomer (I VDF SO3X ), the amount of these repeating units (3) is usually 0 mol% to 30 mol%, preferably 0 mol% to 15 mol%.

[0093] According to certain embodiments, the preferred ionomer (I VDF SO3X ) is a polymer typically consisting essentially of:

[0094] (1) from 55 mol% to 95 mol%, preferably from 70 mol% to 92 mol% of repeating units derived from VDF;

[0095] (2) from 5 mol% to 40 mol%, preferably from 8 mol% to 30 mol% of at least one -SO3X as described in detail above a groups and are derived from hydrolyzed repeat units of at least one (plural) monomer(s) (2);

[0096] (3) from 0 to 15 mol %, preferably from 0 to 10 mol %, of repeating units (3) derived from hydrogenated monomer(s) or fluorinated monomer(s) other than VDF, as detailed above,

[0097] The above items are as follows: VDF SO3X ) is based on the total moles of repeating units.

[0098] Ionomer (I X ) and / or its precursor (I P ) may further comprise repeating units derived from at least one bis-olefin [bis-olefin (OF)] having the formula:

[0099] R AR B =CR C -T-CR D =R E R F

[0100] Among them, R A 、R B 、R C 、R D 、R E and R F is selected from the group consisting of: H, F, Cl, C1-C5 alkyl and C1-C5 (per)fluoroalkyl, and T is: a linear or branched C1-C5 alkyl group, optionally comprising one or more than one ether oxygen atom, preferably at least partially fluorinated 18 an alkylene group or a cycloalkylene group; or a (per)fluoropolyoxyalkylene group.

[0101] The bis-olefin (OF) is preferably selected from the group consisting of those having any one of formulae (OF-1), (OF-2) and (OF-3):

[0102] (OF-1)

[0103]

[0104] wherein j is an integer comprised between 2 and 10, preferably between 4 and 8, and R1, R2, R3 and R4, which are equal to or different from each other, are chosen from the group consisting of H, F, C1-C5 alkyl and C1-C5 (per)fluoroalkyl;

[0105] (OF-2)

[0106]

[0107] wherein each A, which is equal to or different from each other at each occurrence, is independently selected from the group consisting of H, F, and Cl; each B, which is equal to or different from each other at each occurrence, is independently selected from the group consisting of H, F, Cl, and OR B The group consists of R B is a branched or straight chain alkyl group which may be partially, substantially or completely fluorinated or chlorinated, and E is an optionally fluorinated divalent group having 2 to 10 carbon atoms which may be interrupted by an ether bond; preferably, E is -(CF2) m - group, wherein m is an integer comprised between 3 and 5; a preferred bis-olefin of the (OF-2) type is F2C=CF-O-(CF2)5-O-CF=CF2;

[0108] (OF-3)

[0109]

[0110] wherein E, A and B have the same meanings as defined above, and R5, R6 and R7, which are equal to or different from each other, are selected from the group consisting of H, F, C1-C5 alkyl and C1-C5 (per)fluoroalkyl.

[0111] If the ionomer (I X ) or its precursor (I P ) further comprises repeating units derived from at least one bis-olefin (OF), then, as the case may be, the ionomer (I X ) or its precursor (I P ) typically comprises ionomers (I X ) or its precursor (I P ) comprises repeating units derived from said at least one bis-olefin (OF) in an amount between 0.01 mol % and 1.0 mol %, preferably between 0.03 mol % and 0.5 mol %, more preferably between 0.05 mol % and 0.2 mol %, based on the total moles of repeating units of ).

[0112] As the case may be, the ionizable or hydrolyzable groups in the ionomer (I X ) or its precursor (I P ) should be such as to provide relative to the ionomer (I X ) or precursor (I P ) has a total weight of at least 0.55 meq / g, preferably at least 0.65 meq / g, more preferably at least 0.75 meq / g of ionizable or hydrolyzable groups.

[0113] About ionomers (I X ) or precursor (I P ) is included in the maximum amount of said ionizable or hydrolyzable groups, there is no substantial limit. It is generally understood that, as the case may be, relative to the ionomer (I X ) or precursor (I P ), the ionizable or hydrolyzable groups are typically present in an amount of at most 3.50 meq / g, preferably at most 3.20 meq / g, more preferably at most 2.50 meq / g.

[0114] In step (1) of the method of the present invention, a method comprising a precursor (I P ) of the original polymerized aqueous latex of particles.

[0115] The expression "as-polymerized aqueous latex" is hereby given its common meaning in the art and designates an aqueous dispersion comprising stably dispersed polymer particles obtained from emulsion polymerization. The particular emulsion polymerization technique used to produce the latex is not particularly limited. Techniques in which the latex is produced by emulsion polymerization in an aqueous medium in the presence of one or more emulsifiers and techniques in which no emulsifier is used may be equally effective.

[0116] For use in the manufacture of latex (I P ) in an aqueous polymerization medium and may be included in the latex (I p ) in the emulsifier, specifically non-limiting examples of fluorinated emulsifiers include, among others, the following:

[0117] (a')CF3(CF2) n0 COOM', wherein n0 is an integer ranging from 4 to 10, preferably from 5 to 7, preferably n0 is equal to 6, and M' represents NH4, Na, Li or K, preferably NH4;

[0118] (b')[R1-O n -LA - ]Y +

[0119] wherein: R1 is a linear or branched aliphatic group which may contain a partially or fully fluorinated ether bond; n is an integer; L is a linear or branched alkylene group which may be non-fluorinated, partially fluorinated or fully fluorinated and may contain an ether bond; A - is an anionic group selected from the group consisting of carboxylate, sulfonate, sulfonamide anion and phosphonate; and Y + is hydrogen, ammonium or an alkali metal cation; from class (b') the following may be specifically mentioned:

[0120] (b'-1)T-(C3F6O) n1 (CFYO) m1 CF2COOM", wherein T represents a Cl atom or a x F 2x+1-x' Cl x' O, wherein x is an integer ranging from 1 to 3 and x' is 0 or 1, n1 is an integer ranging from 1 to 6, m1 is 0 or an integer ranging from 1 to 6, M" represents NH4, Na, Li or K and Y represents F or -CF3;

[0121] (b'-2)R f -(OCF2CF2) k-1 -O-CF2-COOX a (IA)

[0122] Among them, R f is a C1-C3 perfluoroalkyl group optionally including one or more ether oxygen atoms, k is 2 or 3 and X a Selected from monovalent metals and having the formula NR N 4, wherein R is the same or different at each occurrence N is a hydrogen atom or a C1-C3 alkyl group;

[0123] (b'-3)F-(CF2CF2) n2 -CH2-CH2-X * O3M"', where X * is a phosphorus or sulfur atom, preferably, X * is a sulfur atom, M'' represents NH4, Na, Li or K and n2 is an integer ranging from 2 to 5, preferably, n2 is equal to 3;

[0124] (c')AR bf -B bifunctional fluorinated surfactant, wherein A and B, which are equal to or different from each other, have the formula -(O) p CFY”-COOM * , where M * represents NH4, Na, Li or K, preferably, M * represents NH4, Y" is F or -CF3 and p is 0 or 1, and R bf is a divalent (per)fluoroalkyl chain or (per)fluoropolyether chain, such that AR bf - the number average molecular weight of B is in the range of from 300 to 1800;

[0125] (d') a cyclic fluorine compound having the formula (II):

[0126]

[0127] wherein X1, X2 and X3, which are equal to or different from each other, are independently selected from the group consisting of H, F and a C1-C6 (per)fluoroalkyl group optionally including one or more chain or non-chain oxygen atoms, L is a bond or a divalent group, R F is a divalent fluorinated C1-C3 bridging group, and Y is an anionic functional group; and

[0128] (e') mixtures thereof

[0129] The latex is an aqueous latex, that is, wherein the precursor (I P ) is an aqueous medium, that is to say a medium consisting mainly of water; however, small amounts of other solvents and / or components / auxiliaries used in the polymerization reaction (residues of initiators, chain transfer agents, stabilizers, emulsifiers) may be present in the latex.

[0130] In step (2), in the case of the group -SO2X X 、-PO2X X and-COX x At least partially converted into the corresponding group -SO3X a 、-PO3X a and-COOX a Without causing any significant coagulation, the latex (I x ) is contacted with an alkaline hydrolyzing agent [reagent (B)] to obtain an ionomer (I X ) particles of aqueous latex, wherein X x is F or Cl, where X a is H, an ammonium group or a metal, preferably a monovalent metal.

[0131] There is no particular limitation on the selection of the alkaline hydrolysis agent, provided that the alkaline hydrolysis agent can effectively induce the desired hydrolysis reaction.

[0132] Typically, an inorganic base, particularly an inorganic hydroxide of an alkali metal or alkaline earth metal, may be used, but organic bases may also be effective for this purpose. Among the inorganic bases that have been found useful, mention may be made of KOH, NaOH, LiOH, Mg(OH) 2 , Ca(OH) 2 .

[0133] Typically, the reagent (B) is used in excess relative to the total amount of equivalents of the groups to be hydrolyzed.

[0134] In particular, the temperature and stirring in step (2) and the total concentration of reagent (B) are controlled to prevent the original latex (I P ) and the resulting latex (I X ) any significant condensation.

[0135] However, it is understood that a small amount of coagulum and / or sediment formation may occur: the coagulation in step (2) results in a smaller amount of coagulum and / or sediment formation than the original latex (I P ) or the obtained latex (I X ) is suitable as an example in which any significant coagulum has formed.

[0136] During step (2), advantageously, the raw latex (I p ) in the precursor (I p ) has not been significantly modified, so that it can be said that advantageously, the particles dispersed in the obtained latex (I X ) in the ionomer (I x ) of the particles dispersed in the original latex (Ip ) in the precursor (I p ) are substantially identical to one of the particles.

[0137] Typically, the dispersion in the original latex (I p ) in the precursor (I p ) has an average particle size advantageously in the range of 15 nm to 150 nm; more particularly, said average particle size is advantageously at least 30 nm, preferably at least 50 nm and / or advantageously at most 140 nm, preferably at most 120 nm, more preferably at most 100 nm.

[0138] Similarly, dispersed in the obtained latex (I X ) in the ionomer (I X ) has an average particle size advantageously in the range of 15 nm to 150 nm; more particularly, said average particle size is advantageously at least 30 nm, preferably at least 50 nm and / or advantageously at most 140 nm, preferably at most 120 nm, more preferably at most 100 nm.

[0139] Dispersed in latex (I p ) and / or latex (I X ) can be measured by photon correlation spectroscopy (PCS), a method also known as dynamic laser light scattering (DLLS) technique, in particular according to the method described in B. Chu "Laser light scattering" Academic Press, New York (1974) in accordance with ISO 13321.

[0140] It is well known to those skilled in the art that PCS gives an estimate of the mean hydrodynamic diameter. For the purposes of the present invention, the term "mean particle size" shall be intended to have its broadest meaning in relation to the determination of the hydrodynamic diameter. It will also be understood that, for the purposes of ISO 13321, the term "mean particle size" of the primary particles is intended to mean the particle diameter X averaged by the harmonic intensity. PCS , as determined by equation (C.10) of Annex C of ISO 13321.

[0141] As an example, the average primary particle size can be measured using a 10 mV He-Ne laser source and PCS software (Malvern version 1.34) by using a Malvern Zetasizer 3000HS device at a 90° scattering angle. The average particle size is preferably measured on latex samples that are appropriately diluted with redistilled water and filtered on a 0.2 μm Millipore filter.

[0142] Step (2) may further comprise: in realizing the reaction between the reagent (B) and the latex (I P ) after contact between the latex (I X ) is contacted with at least one neutralizing agent [agent (N)] different from agent (B). The choice of agent (N) is not particularly limited; generally, this step of contacting with agent (N) effectively restores the latex (I X ) of the ionizable groups, i.e., the -SO3H, -PO3H and -COOH forms of these ionizable groups, as appropriate. Reagents (N) that have been found to be useful include organic acids and inorganic acids.

[0143] Therefore, the result of step (2) of the process of the present invention is a latex (I X ), the latex (I X ) may include reagent (B) residues and / or other contaminants. The expression "contaminants" is hereby understood to encompass residues other than ionomer (I X ) other than those that can be dissolved / contained in latex (I X ) in the aqueous medium. Exemplary embodiments of these ingredients / compounds may be derived from P ) of polymerization initiators, suspending agents, emulsifiers, buffers and other adjuvant residues, which are actually known to be in the latex (I X ) exists in the form of ionized / ionizable species.

[0144] According to certain embodiments, therefore, for the method of the present invention, comprising making the latex (I x ) may be suitable as a step (3) of contacting the reagent (B) with at least one ion exchange resin in order to at least partially remove residues of said reagent (B) and / or other contaminants.

[0145] In the remainder of this text, for the purposes of the present invention, the expression "ion exchange resin" is to be understood in the plural and singular and is intended to mean a solid insoluble matrix (or support structure), usually in the form of beads of reduced size (e.g., from 0.1 mm to 5 mm), usually made from an organic polymer substrate, on the surface of which there are active sites (ion exchange sites) that readily capture and release (i.e., exchange) ions in a process known as ion exchange.

[0146] Ion exchange does not typically undergo structural changes during the ion exchange step (3).

[0147] Ion exchange resins may be natural or synthetic substances that can exchange their own ions for ions present in the liquid with which they come into contact.

[0148] Therefore, during step (3), the ions are advantageously present in the latex (I X ) is exchanged with an ion exchange resin. Thus, for example, it is advantageous to P ) of any emulsifier anion from latex (I X ) is transferred to the ion exchange resin. At the same time, the anions initially bound to the ion exchange resin are advantageously transferred to the latex (I X ).

[0149] Ion exchange resins are typically composed of synthetic beads. Each bead is a polymer matrix containing ion exchange sites on the surface and within the matrix itself.

[0150] The polymer matrix of ion exchange resin preferably comprises the repeating unit derived from styrene (so-called polystyrene matrix) or the repeating unit derived from (methyl) propionate (so-called acrylic matrix).Required exchange site can be introduced after polymerization, or substituted monomer can be used.The polymer matrix is ​​preferably a cross-linked matrix.Crosslinking is usually achieved by adding a small proportion of divinylbenzene during polymerization.Because non-cross-linked polymer depends on the tendency of the combined ion to change size, non-cross-linked polymer is hardly used.More preferably, the polymer matrix is ​​a cross-linked polystyrene matrix.

[0151] There are many different types of ion exchange resins that are made to selectively prefer one or a few different types of ions.

[0152] Anions can only be exchanged with other anions and cations with other cations. Therefore, the ion exchange resins used are specifically designed for the exchange of ions from latex (I X It will also be appreciated that the contaminants / residues may be adsorbed onto the ion exchange resin according to a mechanism other than ion exchange.

[0153] Anion exchange resins have positively charged ion exchange sites to which anions are attached, and cation exchange resins have negatively charged ion exchange sites to which cations are attached. Ion exchange resins are typically initially attached to ions that have a low affinity for these exchange sites. X ) contact an ion exchange resin, the anions with the greatest affinity for the exchange sites generally displace those with the lowest affinity. Therefore, it is important that the ion exchange resin contain anions with a lower affinity than those that are to be exchanged. Due to their low affinity for the exchange sites, anion exchange resins are often used with chloride (Cl - ) or hydroxyl group (OH - )ion.

[0154] Preferably, the ion exchange resin used in step (3) of the process of the present invention comprises at least one anion exchange resin as defined above, in order to remove anionic contaminants / residues as detailed above. P ) when the emulsifier used is a metal or quaternary ammonium salt of anionic (preferably fluorinated) species, therefore, anion exchange resins are generally considered to be more appropriate for their chelation and removal.

[0155] Non-limiting examples of positively charged ion exchange sites of anion exchange resins are depicted below:

[0156]

[0157] wherein R, which is the same or different at each occurrence, is independently C1-C 12 A hydrocarbon group or a hydrogen atom, and E, which is the same or different at each occurrence, is independently a divalent hydrocarbon group comprising at least one carbon atom.

[0158] Preferably, the positively charged ion exchange sites of the anion exchange resin are selected from the following:

[0159]

[0160] The choice of anion that binds to the positively charged ion exchange sites is not critical, provided that the anion typically has less affinity for the sites relative to the anion of the contaminant / residue to be removed.

[0161] Anion exchange resins preferably have attached to their positively charged ion exchange sites anions selected from the group consisting of: - (HF's pKa is 3.17); OH - (The pKa of H2O is 15.75); CH3O - (The pKa of CH3OH is 15.5); (CH3)2CHO - ((CH3)2CHOH has a pKa of 16.5); (CH3)3CO - (The pKa of (CH3)3COH is 17).

[0162] The anion exchanger has a counterion corresponding to an acid having a pKa value of preferably at least 5 (still more preferably at least 7).

[0163] The most preferred counterion is OH - .

[0164] In step (3), once the latex (I X) has been in contact with an anion exchange resin, the resin beads typically adsorb to or bind to their positively charged ion exchange sites, undesirable anions of contaminants / residues, and the original ions attached to the beads can be removed in the purified latex (I X ) was found in .

[0165] If the anion exchange resin includes OH groups bound to its positively charged ion exchange sites - anion, then the OH - The anions are usually ultimately present in the purified aqueous dispersion. X ) may experience a perceptible pH increase. Depending on the intended use, and of course also to avoid coagulation phenomena, a pH adjustment may be necessary.

[0166] Step (3) may include contacting the latex (IX) with a cation exchange resin; step (3) may include such contacting with the cation exchange resin before, after, or instead of contacting with the anion exchange resin. However, in order to thoroughly remove residues / contaminants and to ensure that the ionizable groups are provided in an appropriate form, the contacting with the cation exchange resin occurs after the contacting with the anion exchange resin.

[0167] Non-limiting examples of negatively charged ion exchange sites of cation exchange resins suitable for use in the methods of the present invention are depicted below:

[0168]

[0169] The choice of cations to be bound to the negatively charged ion exchange sites is not critical, provided that the cations are present relative to those included in the latex (I X ) that must be removed, which cation typically has less affinity for the site. For example, cation exchange resins typically have sodium (Na + ) or hydrogen (H + ) ions. Both of these ions have a low affinity for the sites. Almost any cation that comes into contact with the cation exchange resin has a greater affinity and replaces the hydrogen or sodium ion at the exchange site.

[0170] Cation exchange resins preferably attach hydrogen (H) to their negatively charged anion exchange sites. + )ion.

[0171] If the cation exchange resin includes H bound to its negatively charged ion exchange sites + cation, then the H + The cations are usually present in the latex (I X ), and therefore, with H +This contact of the cation exchange resin with the cations effectively ensures that the ionomer (I X ) are in their acid form, ie in their -SO3H, -PO3H and -COOH form, as the case may be.

[0172] Therefore, the latex (I X ) and with hydrogen (H + ) cation exchange resin contact can reduce the latex (I X ), which may require adjustment of the pH by known means.

[0173] In step (4), the latex (I X ) for spray drying.

[0174] Spray drying is a well-known technique for converting liquid solutions / suspensions into dry powders by evaporating the liquid medium from droplets dispersed in a drying chamber and in contact with a drying gas stream.

[0175] Therefore, step (4) of the method of the present invention comprises the step of subjecting the latex (I x ) through a nozzle to generate droplets thereof and disperse the droplets in a drying chamber.

[0176] Any type of nozzle may be used, including, among others, pressure nozzles, where the droplet size can be adjusted based on the orifice size and pressure, or rotary atomizers, where the droplet size can be adjusted based on the rotating element diameter and rotational speed.

[0177] As the drying gas, a heated air stream may advantageously be used in step (4), but other gases such as, in particular, nitrogen may also be equally effective.

[0178] The direction of flow of the drying gas can be parallel or countercurrent relative to the flow of the droplets, which is in a vertically downward direction as achieved by gravity. In order to optimize the size distribution of the material (P), a combination of parallel and countercurrent drying gas flows may be preferred.

[0179] In step (4), the droplets of latex (Ix) are advantageously dried using a drying gas at a temperature such that the temperature in the drying chamber is at least 50° C., preferably at least 60° C., more preferably at least 80° C., most preferably at least 85° C. In order to avoid the latex (Ix) X ), the temperature of the drying gas in step (4) is usually adjusted so that the temperature of the drying chamber is at most 125° C., preferably at most 120° C., more preferably at most 115° C. Ideally, a drying gas which maintains the drying chamber temperature between 90° C. and 110° C. would be preferred.

[0180] The result of the process of the present invention is a polymer composed of a plurality of ionomers (I X ) particles [material (P)], which is another object of the present invention.

[0181] The material (P) of the present invention consists of particles in the form of hollow agglomerates, the average particle size of these particles being between 1 μm and 150 μm; preferably, the average particle size of the particles is at least 3 μm, more preferably at least 5 μm and / or at most 100 μm, preferably at most 50 μm, even more preferably at most 40 μm.

[0182] Furthermore, the material (P) is composed of quasi-spherical particles.

[0183] Quasi-spherical according to the present invention means that the particles have a spherical or nearly spherical shape. Geometrically, a sphere is described by axes of the same length, which start from a common starting point and are directed into space and define the radius of the sphere in all spatial orientations. Therefore, spherical particles are particles whose shape meets this geometric requirement. On the other hand, in quasi-spherical particles, the length of the axis that characterizes its shape can deviate from the ideal spherical shape by 1% to 40%. Preferably, quasi-spherical particles with a deviation of at most 25%, particularly preferably at most 15%, are obtained. The quasi-spherical or spherical shape of the particles can be determined by image analysis of an appropriate magnification obtained by microscopy (e.g., electron microscopy).

[0184] The particles are hollow agglomerates of elementary particles. In fact, their hollow nature can be demonstrated by using scanning electron microscopy: while taking magnification pictures of the hollow agglomerates before and after compression with sufficient pressure intensity, it can be easily demonstrated that the hollow agglomerates collapse, confirming their hollow nature.

[0185] Analysis of the images at microscopic magnifications showed that the quasi-spherical particles were in fact X )'s basic particles corresponding to the agglomerates of basic particles.

[0186] More particularly, the average diameter of the elementary particles is between 15 nm and 150 nm; more particularly, the average diameter is advantageously at least 30 nm, preferably at least 50 nm and / or advantageously at most 140 nm, preferably at most 120 nm, more preferably at most 100 nm.

[0187] The average diameter of the elementary particles can be determined by scanning electron microscopy followed by image analysis. A section of the magnified image is examined visually or with computer assistance, and the elementary particles are counted. The counted particles are modeled as spheres with the smallest diameter, which provides the sphere surrounding the elementary particles, as the diameter. Thus, the average diameter is determined as the arithmetic mean.

[0188] The above description of the method of the present invention in combination with the ionomer (I X All the characteristics already disclosed are also applicable to the ionomer (I) of the material (P) of the present invention. X ) characteristics.

[0189] The present invention further relates to a method for providing a coating composition, said method comprising contacting a material (P) as described above in detail with a liquid medium.

[0190] The choice of liquid medium is not particularly limited; organic solvents can be used, but aqueous coating compositions are preferred, wherein the liquid medium includes water, and preferably includes water as the main component. Small amounts of organic solvents, such as alcohols, particularly aliphatic alcohols (typically including diols or polyols), can be included in the liquid medium of the aqueous coating composition.

[0191] The coating compositions thus obtained can be used to coat and / or impregnate a variety of supports.

[0192] Thus, within the scope of the present invention are also methods of coating or impregnating a support, which methods comprise the use of a coating composition comprising a liquid medium and a material (P) as detailed above.

[0193] Should the disclosure of any patents, patent applications, and publications incorporated herein by reference conflict with the description of the present application to the extent that a term is unclear, the present description shall take precedence.

[0194] The present invention will now be described with reference to the following examples, which are merely illustrative in scope and are not intended to limit the scope of the invention.

[0195] Material :

[0196] Preparation Example 1 - Preparation of TFE-VEFS polymer latex in the form of SO2F

[0197] The following reagents were placed in a 22 L autoclave:

[0198] -9.3L of demineralized water;

[0199] - 700 g of a monomer having the formula: CF2=CF-O-CF2CF2-SO2F (VEFS);

[0200] -650g of 5wt% ClF2O (CF2CF(CF3)O) n (CF2O) m CF2COOK aqueous solution (average molecular weight = 521, n / m ratio = 10).

[0201] The autoclave was heated at 66° C. while stirring at 470 rpm. An aqueous solution of potassium persulfate containing 9 g / L was added in an amount of 170 ml. The pressure was maintained at a value of 14.4 bar (absolute) by feeding tetrafluoroethylene (TFE). During the polymerization, aliquots of 100 g of VEFS were repeatedly added per 160 g of tetrafluoroethylene in the reactor. After 240 minutes, the reaction was stopped by interrupting stirring, cooling the autoclave and reducing the internal pressure by venting TFE; the total mass of TFE fed into the reactor was 3200 g.

[0202] The solid content of the precursor latex thus obtained was 30 wt%.

[0203] A small sample of the latex was then coagulated by freezing and thawing, and the recovered polymer was washed with water and dried at 80° C. for 48 hours. The equivalent weight (EW) of the corresponding polymer was determined to be 967 g / mol by FT-IR measurement. The particle size of the polymer particles dispersed in the obtained latex was found to be 50 nm to 100 nm.

[0204] Preparation Example 2—Preparation of TFE-VEFS Water-Based Dispersion

[0205] The precursor latex of Preparation Example 1 was coagulated by freezing and thawing, and the recovered powder was thoroughly washed with water and then dried at 80° C. for 48 hours.

[0206] A portion of the precursor ionomer powder thus obtained (100 g) was first treated with a solution (1 L) of 14 wt% potassium hydroxide, 30 wt% dimethyl sulfoxide and 56 wt% demineralized water at 80° C. under stirring for 8 hours. After washing several times with demineralized water, the solid polymer thus recovered was acidified with 1 L of a 20 wt% nitric acid solution at room temperature for 2 hours. The powder thus obtained was washed again with demineralized water and finally dried in a ventilated oven at 80° C. for 8 hours.

[0207] The quantitative conversion of -SO2F to -SO3H functional groups was confirmed by FT-IR analysis.

[0208] This hydrolyzed ionomer powder (60 g) was mixed with demineralized water (160 g) in a 250 ml titanium autoclave. The mixture was heated to a temperature above 180° C. and stirred at 750 rpm. After 4 hours, the mixture was cooled and the aqueous dispersion was purified by centrifugation (10,000 rpm) for 2 hours. The clear, transparent dispersion of the ionomer had a solids content of 22.7 wt%.

[0209] Preparation Example 3 - Hydrolysis of TFE-VEFS Precursor Latex and Provision of Ionomer Latex

[0210] One liter of the precursor latex prepared in Preparation Example 1 was contacted with 73.5 g of a NaOH / H2O 2 wt% solution at room temperature for 5 days and then with 73.5 g of a NaOH / H2O 20 wt% solution at room temperature for two days.

[0211] The conversion of the original -SO2F group to -SO3Na was assessed by solid-state nuclear magnetic resonance (NMR).

[0212] The mixture was then purified using a Lewatit Monoplus M800 OH anion exchange resin column, followed by a final treatment using a Lewatit Monoplus S 108H cation exchange column. ICP-OES analysis confirmed the complete conversion of the ionizable -SO3Na groups to -SO3H.

[0213] Thus a purified ionomer latex in -SO3H was recovered having a solids content of 15% wt. The particle size of the ionomer particles dispersed in the obtained latex was found to be between 50 nm and 100 nm.

[0214] Comparative Example 4 - Spray Drying of the TFE-VEFS Dispersion from Example 2

[0215] The ionomer dispersion prepared in Preparative Example 2 (200 g) was spray dried in a spray dryer apparatus having a heated air inlet temperature of about 190° C. (resulting in an average drying chamber temperature of about 100° C.) and a co-current two-fluid nozzle with a diameter of 0.7 mm by redispersing the previously coagulated ionomer precursor subjected to solid phase hydrolysis in water to provide a dry powder (about 44 g).

[0216] On microscopic analysis, the particles of the powder obtained were found to be spherical and to have an average particle size of about 30 μm. The particles did not show structuring into agglomerates of elementary particles: instead, they were found to be continuous homogeneous particles.

[0217] Example 5 - Spray Drying of Ionomer Latex from Example 3

[0218] The ionomer latex prepared in Example 3 (200 g) was spray dried in a spray dryer apparatus having a heated air inlet temperature of about 190° C. (resulting in an average drying chamber temperature of about 100° C.) and an integrated co-current two-fluid nozzle of 0.7 mm in diameter to provide a dry powder (about 30 g).

[0219] The particles of the obtained powder were spherical and had an average particle size of about 10 μm; the particles were found to be hollow. Further, each particle was composed of smaller elementary particles having an average diameter of about 80 nm and a diameter range of about 60 nm to about 100 nm.

[0220] Redispersion in water and viscosity measurement of powders from Comparative Example 4 and Example 5

[0221] The powders obtained as described in Comparative Example 4 and Example 5 were dissolved in demineralized water at room temperature with stirring to give two water-based formulations with a solids content of 25 wt%.

[0222] In both cases, the powders dissolved readily and rapidly without measurable solid residues. Viscometer with Couette geometry was used to measure the viscosity from 100 s -1 to 1000s -1 The water-based formulations were subjected to liquid viscosity measurements at room temperature (23° C.) using a shear rate sweep. The results are summarized in the table below.

[0223] Table 1

[0224] <![CDATA[Shear rate (s -1 )]]> Example 4C (Pa×s) Example 5 (Pa×s) 100 0.07 0.13 500 0.01 0.02 1000 0.007 0.01

[0225] The data summarized in the table above well demonstrate that the process of the invention provides powders of the invention that are particularly readily redispersible in aqueous media and capable of delivering liquid formulations having increased liquid viscosity, particularly at low shear rates, to make them compatible with typical coating techniques, without the need for the addition of thickeners or other viscosity enhancers that might normally compromise the overall properties of the coating / dipped article obtained therefrom.

Claims

1. A method for producing a powdered material P, the material P consisting of at least one ionomer I comprising a plurality of ionizable groups X The plurality of particles are composed of the plurality of ionizable groups selected from -SO3X a 、-PO3X a and-COOX a A group consisting of X a is H, the method comprising: Step (1): Providing an initial polymerized aqueous latex I p , the latex I p comprising at least one ionomer precursor I comprising a plurality of hydrolyzable groups P The particles, the plurality of hydrolyzable groups are selected from -SO2X X 、-PO2X X and-COX x A group consisting of X x It is a halogen; Step (2): In order to make the group -SO2X X 、-PO2X X and-COX x At least partially converted into the corresponding group -SO3X a 、-PO3X a and-COOX a Without causing any significant coagulation, the original polymerized aqueous latex I p Contact with reagent B as alkaline hydrolysis agent to obtain ionomer I X Aqueous latex of particles, wherein X x is F or Cl, where X a is H, ammonium or monovalent metal; Step (3): Make the latex I x with H bound to its negatively charged ion exchange sites + The cations are contacted with the cation exchange resin to convert the -SO3X a 、-PO3X a and-COOX a Converted to the corresponding groups -SO3H, -PO3H and -COOH, where X a is H, an ammonium group, or a monovalent metal; and Step (4): the latex I x Spray drying is performed to obtain the material P.

2. The method of claim 1, wherein the step (3) comprises subjecting the latex I x Contacting with at least one anion exchange resin and / or at least one cation exchange resin to at least partially remove reagent B residues and / or other contaminants.

3. The method of claim 1, wherein X x It is F or Cl.

4. The method of any one of claims 1 to 3, wherein the latex 1 p comprising at least one fluorinated emulsifier selected from the group consisting of: (a')CF3(CF2) n0 COOM', where n0 is an integer ranging from 4 to 10, and M' represents NH4, Na, Li or K; (b')[R1-O n -L-A - ]Y + wherein: R1 is a partially or fully fluorinated linear or branched aliphatic group optionally containing an ether bond; n is an integer; L is a linear or branched alkylene group that is optionally non-fluorinated, partially fluorinated or fully fluorinated and optionally contains an ether bond; A - is an anionic group selected from the group consisting of carboxylate, sulfonate, sulfonamide anion and phosphonate; and Y + is hydrogen, ammonium, or an alkali metal cation; (c')AR bf -B bifunctional fluorinated surfactant, wherein A and B, which are equal to or different from each other, have the formula -(O) p CFY”-COOM * , where M * represents NH4, Na, Li or K, Y" is F or -CF3 and p is 0 or 1, and R bf is a divalent fluoroalkyl chain or fluoropolyether chain, making AR bf - the number average molecular weight of B is in the range of from 300 to 1800; (d') a cyclic fluorine compound having the formula (II): wherein X1, X2 and X3, which are equal to or different from each other, are independently selected from the group consisting of H, F and a C1-C6 fluoroalkyl group optionally including one or more chain or non-chain oxygen atoms, L is a bond or a divalent group, R F is a divalent fluorinated C1-C3 bridging group, and Y is an anionic functional group; and (e') mixtures thereof. The method of claim 4 , wherein n 0 is an integer ranging from 5 to 7. The method of claim 4 , wherein n 0 is equal to 6.

7. The method of claim 4, wherein M' represents NH4.

8. The method of claim 4, wherein (b') is selected from the group consisting of: (b'-1)T-(C3F6O) n1 (CFYO) m1 CF2COOM", in which, T represents a Cl atom or a compound having the formula C x F 2x+1-x' Cl x' O, wherein x is an integer ranging from 1 to 3 and x' is 0 or 1, n1 is an integer ranging from 1 to 6, m1 is 0 or an integer ranging from 1 to 6, M" represents NH4, Na, Li or K and Y represents F or -CF3; (b'-2)R f -(OCF2CF2) k-1 -O-CF2-COOX a (IA) Among them, R f is a C1-C3 perfluoroalkyl group optionally including one or more ether oxygen atoms, k is 2 or 3 and X a Selected from monovalent metals and having the formula NR N 4, wherein R is the same or different at each occurrence N is a hydrogen atom or a C1-C3 alkyl group; (b'-3)F-(CF2CF2) n2 -CH2-CH2-X * O3M"', where X * is a phosphorus or sulfur atom, M'' represents NH4, Na, Li or K and n2 is an integer ranging from 2 to 5.

9. The method of claim 8, wherein: X * It's a sulfur atom.

10. The method of claim 8, wherein: n2 is equal to 3.

11. The method of claim 8, wherein: M * Indicates NH4.

12. The method of claim 4, wherein R bf It is a divalent perfluoroalkyl chain or a perfluoropolyether chain.

13. The method of claim 4, wherein X1, X2 and X3, which are equal to or different from each other, are independently selected from the group consisting of H, F and a C1-C6 perfluoroalkyl group optionally including one or more chain or non-chain oxygen atoms.

14. The method according to any one of claims 1 to 3, wherein In step (2), the latex I p With reagent B as alkaline hydrolysis agent, the reagent B is selected from inorganic bases, and / or wherein step (2) optionally further comprises in realizing reagent B and latex I P After the contact between the latex I X It is brought into contact with at least one reagent N which is different from the reagent B and serves as a neutralizing agent.

15. The method of claim 14, wherein: The reagent B is selected from the group consisting of KOH, NaOH, LiOH, Mg(OH)2 and Ca(OH)2.

16. The method according to any one of claims 1 to 3, comprising: Make the latex I x contacting with at least one ion exchange resin to at least partially remove said reagent B residues and / or other contaminants (3); and wherein said ion exchange resin comprises at least one anion exchange resin, wherein the positively charged ion exchange sites of said anion exchange resin are selected from the group consisting of: wherein R, which is the same or different at each occurrence, is independently C1-C 12 A hydrocarbon group or a hydrogen atom, and E, which is the same or different at each occurrence, is independently a divalent hydrocarbon group comprising at least one carbon atom.

17. The method of claim 16, wherein: Step (3) comprises subjecting the latex I to a reaction mixture before or after contact with an anion exchange resin. X The step of contacting with a cation exchange resin, and wherein the negatively charged ion exchange sites of the cation exchange resin are selected from the group consisting of:

18. The method of claim 1, wherein the powdered material P is composed of at least one fluorinated ionomer I comprising a plurality of ionizable groups. X The plurality of particles are composed of the plurality of ionizable groups selected from -SO3X a 、-PO3X a and-COOX a A group consisting of X a It's H. The particles are present in quasi-spherical hollow agglomerates of elementary particles; - the average particle size of the hollow agglomerates is from 1 μm to 150 μm; and - The average diameter of the primary particles is between 15 nm and 150 nm.

19. The method of claim 18, wherein: Ionomer I X comprising repeating units derived from an ethylenically unsaturated monomer comprising at least one fluorine atom and optionally further comprising repeating units derived from at least one hydrogenated monomer, and / or wherein, Ionomer I X A copolymer comprising said ionizable groups as pendant groups covalently bonded to hydrolyzable repeating units derived from a functional monomer X and optionally consisting of a sequence of hydrolyzable repeating units derived from one or more than one monomer X or optionally comprising hydrolyzable repeating units derived from one or more than one monomer X and repeating units derived from one or more than one further monomer different from monomer X, wherein monomer X is a fluorinated monomer.

20. The method according to any one of claims 18 to 19, wherein Ionomer I X Yes and includes multiple -SO3X a Ionomer I SO3X , and: derived from the formula -SO3X a At least one group of one or more than one monomer X SO3X The sequence is composed of multiple repeating units, wherein X a is H; or comprises one or more monomers X SO3X Multiple repeating units and derived from monomers other than X SO3X The invention also provides repeating units of one or more than one additional monomer.

21. The method of claim 20, wherein: Ionomer I SO3X Selected from the group consisting of polymers consisting of: a plurality of hydrolyzable repeating units comprising at least one -SO3X a Group, where X a is H; and is derived from a compound comprising at least one -SO2X X at least one ethylenically unsaturated fluorinated monomer A, wherein X x Is a halogen; and a plurality of repeating units, the plurality of repeating units being derived from at least one non-SO2X X The ethylenically unsaturated fluorinated monomer B of the group.

22. The method of claim 20, wherein: Monomer A is selected from the group consisting of: - sulfonyl halofluoroolefin having the formula: CF2=CF(CF2) p SO2X X , where X X is a halogen, wherein p is an integer between 0 and 10; -sulfonyl halide fluorovinyl ether having the formula: CF2=CF-O-(CF2) m SO2X X , where X X is a halogen, wherein m is an integer between 1 and 10; - sulfonyl fluoride alkoxy vinyl ether having the formula: CF2=CF-(OCF2CF(R F1 )) w- O-CF2(CF(R F2 )) y SO2X X , where X X is a halogen; wherein w is an integer between 0 and 2, and R F1 and R F2 is independently F, Cl or C optionally substituted with one or more ether oxygens 1- C 10 Fluoroalkyl, y is an integer between 0 and 6; - having the formula CF2=CF-Ar-SO2X X Sulfonyl halide aromatic fluoroolefin, wherein X X is a halogen, wherein Ar is C5-C 15 Aromatic or heteroaromatic groups.

23. The method of claim 22, wherein: X X It is F or Cl.

24. The method of claim 22, wherein: X X It's F.

25. The method of claim 22, wherein: Monomer A is selected from the group consisting of sulfonyl halofluoroolefins having the formula: CF2=CF(CF2) p SO2X X , where p is an integer between 1 and 6.

26. The method of claim 25, wherein: p is equal to 2 or 3.

27. The method of claim 22, wherein: Monomer A is selected from sulfonyl halofluoro vinyl ethers having the formula: CF2=CF-O-(CF2) m SO2X X , where m is an integer between 1 and 6.

28. The method of claim 27, wherein: m is an integer between 2 and 4.

29. The method of claim 27, wherein: m is equal to 2.

30. The method of claim 22, wherein: Monomer A is selected from sulfonyl fluoride alkoxy vinyl ether having the formula: CF2=CF-(OCF2CF(R F1 )) w- O-CF2(CF(R F2 )) y SO2X X , where w is 1, R F1 is -CF3, y is 1 and R F2 It's F.

31. The method of claim 22, wherein: Monomer A is selected from the group consisting of monomers having the formula CF2=CF-O-(CF2) m -SO2F, wherein m is an integer between 1 and 6.

32. The method of claim 22, wherein: Monomer A is selected from the group consisting of monomers having the formula CF2=CF-O-(CF2) m -SO2F, wherein m is an integer between 2 and 4.

33. The method of claim 22, wherein: Monomer A is CF2=CFOCF2CF2-SO2F.

34. The method of claim 20, wherein: Monomer (B) is selected from the group consisting of: -C2-C8 perfluoroolefins; -C2-C8 hydrogen-containing fluoroolefins; - C2-C8 chlorine- and / or bromine- and / or iodine-containing fluoroolefins; - having the formula CF2=CFOR f1 Fluoroalkyl vinyl ether, wherein R f1 is a C1-C6 fluoroalkyl group; - a fluoroalkyl vinyl ether of the formula CF2=CFOX0, wherein X0 is a C1-C 12 Fluorooxyalkyl; - Fluorodioxole having the formula: Among them, R f3 、R f4 、R f5 、R f6 wherein each of which is independently a fluorine atom, optionally comprising one or more oxygen atoms, a C1-C6 fluoro(halo)fluoroalkyl group; and - mixtures thereof.

35. The method of claim 34, wherein: The C2-C8 perfluoroolefin is selected from tetrafluoroethylene, hexafluoropropylene, and perfluoroisobutylene.

36. The method of claim 34, wherein: The C2-C8 hydrogen-containing fluoroolefin is selected from trifluoroethylene, vinylidene fluoride, vinyl fluoride, pentafluoropropylene and hexafluoroisobutylene.

37. The method of claim 34, wherein: The C2-C8 chlorine- and / or bromine- and / or iodine-containing fluoroolefin is selected from chlorotrifluoroethylene and bromotrifluoroethylene.

38. The method of claim 34, wherein: R f1 Selected from -CF3, -C2F5, -C3F7.

39. The method of claim 34, wherein: Fluorooxyalkyl vinyl ethers having the formula CF2=CFOX0 include fluoroalkyl vinyl ethers having the formula CF2=CFOCF2OR f2 Fluoromethoxyalkyl vinyl ether, wherein R f2 It is a C1-C3 fluoroalkyl group or a C1-C3 fluorooxyalkyl group.

40. The method of claim 39, wherein R f2 Selected from -CF2CF3, -CF2CF2-O-CF3 and -CF3.

41. The method of claim 34, wherein: R that is the same or different from each other f3 、R f4 、R f5 、R f6 Each of which is independently selected from -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3.

42. The method of claim 34, wherein: Monomer B is selected from the following: - C2-C8 perfluoroolefins selected from tetrafluoroethylene and / or hexafluoropropylene; - a C2-C8 hydrogen-containing fluoroolefin selected from trifluoroethylene, vinylidene fluoride and vinyl fluoride; and - mixtures thereof.

43. The method of claim 34, wherein: At least one monomer B is tetrafluoroethylene, and wherein the ionomer I TFE SO3X A polymer selected from the group consisting of: (1) Repeating units derived from tetrafluoroethylene, relative to ionomer I TFE SO3X The total molar amount of these repeating units 1 is 50 mol% to 99 mol%; (2) Includes at least one -SO3X a groups and derived from hydrolyzed repeating units of at least one monomer selected from the group consisting of: (j) Sulfonyl halide fluorovinyl ether having the formula: CF2=CF-O-(CF2) m SO2X X , where X X is a halogen; wherein m is an integer between 1 and 10; (jj) Sulfonyl fluoride alkoxy vinyl ether having the formula: CF2=CF-(OCF2CF(R F1 )) w -O-CF2(CF(R F2 )) y SO2X X , where X X is a halogen; wherein w is an integer between 0 and 2, and R F1 and R F2 is independently F, Cl or C optionally substituted with one or more ether oxygens 1- C 10 fluoroalkyl, y is an integer between 0 and 6; and (jjj) mixtures thereof; Relative to ionomer I TFE SO3X The amount of these repeating units 2 is 1 mol% to 50 mol% of the total moles of repeating units; and (3) optionally, derived from at least one hydrogenated monomer and / or fluorinated monomer other than tetrafluoroethylene; relative to ionomer I TFE SO3X The amount of these repeating units 3 is 0 mol% to 45 mol% of the total moles of the repeating units.

44. The method of claim 43, wherein: Relative to ionomer I TFE SO3X The amount of these repeating units 1 is 52 mol% to 98 mol% based on the total moles.

45. The method of claim 43, wherein: Relative to ionomer I TFE SO3X The amount of these repeating units 2 is 2 mol% to 48 mol% of the total moles of the repeating units.

46. ​​The method of claim 43, wherein The at least one hydrogenated monomer and / or fluorinated monomer different from tetrafluoroethylene is a perfluorinated monomer selected from the group consisting of: hexafluoropropylene; a monomer having the formula CF2=CFOR' f1 Perfluoroalkyl vinyl ether, wherein R' f1 Is a C1-C6 perfluoroalkyl group; having the formula CF2=CFOR' O1 Perfluoroalkyl vinyl ether, wherein R' O1 It is a C2-C 12 Perfluoroalkyl.

47. The method of claim 46, wherein R' f1 Selected from -CF3, -C2F5, -C3F7.

48. The method of claim 46, wherein With the formula CF2=CFOR' O1 Perfluoroalkyl vinyl ethers include those having the formula CF2=CFOCF2OR' f2 Perfluoroalkyl-methoxy-vinyl ether, wherein R' f2 is a C1-C6 perfluoroalkyl group; or a C1-C6 perfluorooxyalkyl group having one or more ether groups.

49. The method of claim 48, wherein R' f2 Selected from -CF3, -C2F5, -C3F7.

50. The method of claim 48, wherein C1-C6 perfluorooxyalkyl having one or more ether groups is -C2F 5- O-CF3.

51. The method of claim 43, wherein: Relative to ionomer I TFE SO3X The amount of these repeating units 3 is 0 mol% to 40 mol% of the total moles of the repeating units.

52. The method of claim 43, wherein: Ionomer I TFE SO3X It consists of the following: (k) from 55 mol % to 95 mol % of repeating units derived from tetrafluoroethylene; (kk) from 5 mol% to 45 mol% of at least one -SO3X a group and is derived from the hydrolyzed repeating unit of one or more monomers2; (3) from 0 mol% to 25 mol% of repeating units 3 derived from one or more fluorinated monomers other than tetrafluoroethylene, the above items being as described in the ionomer 1 TFE SO3X The total moles of repeating units are calculated.

53. The method of claim 52, wherein the repeating units derived from tetrafluoroethylene are present in the ionomer 1 TFE SO3X The total moles of the repeating units are from 65 mol % to 93 mol %.

54. The method of claim 52, wherein at least one -SO3X a Group and derived from the hydrolyzed repeating units of one or more monomers 2 according to the ionomer 1 TFE SO3X The total moles of the repeating units are from 7 mol% to 35 mol%.

55. The method of claim 52, wherein the repeating units 3 derived from one or more fluorinated monomers other than tetrafluoroethylene are present in the ionomer 1. TFE SO3X The total moles of the repeating units are from 0 mol % to 20 mol %.

56. The method of claim 34, wherein At least one monomer B is vinylidene fluoride, and wherein the ionomer I VDF SO3X A polymer selected from the group consisting of: (1) Repeating units derived from vinylidene fluoride, relative to ionomer I VDF SO3X The total moles of repeating units, the amount of these repeating units 1 is 55 mol% to 99 mol%; (2) Includes at least one -SO3X a groups and derived from hydrolyzed repeating units of at least one monomer selected from the group consisting of: (j) Sulfonyl halide fluorovinyl ether having the formula: CF2=CF-O-(CF2) m SO2X X , where X X is a halogen, wherein m is an integer between 1 and 10; (jj) Sulfonyl fluoride alkoxy vinyl ether having the formula: CF2=CF-(OCF2CF(R F1 )) w -O-CF2(CF(R F2 )) y SO2X X where X X is halogen, wherein w is an integer between 0 and 2, and R F1 and R F2 is independently F, Cl or C1-C1 optionally substituted with one or more ether oxygens 10 fluoroalkyl, y is an integer between 0 and 6; and (jjj) mixtures thereof; Relative to ionomer I VDF SO3X The amount of these repeating units 2 is 1 mol% to 45 mol% of the total moles of repeating units; and (3) optionally, repeating units derived from at least one hydrogenated monomer or fluorinated monomer other than vinylidene fluoride; relative to ionomer I VDF SO3X The amount of these repeating units 3 is 0 mol% to 30 mol% of the total moles of the repeating units.

57. The method of claim 56, wherein: Relative to ionomer I VDF SO3X The amount of these repeating units 1 is 70 mol% to 95 mol% of the total moles of the repeating units.

58. The method of claim 56, wherein Relative to ionomer I VDF SO3X The amount of these repeating units 2 is 5 mol% to 30 mol% of the total moles of the repeating units.

59. The method of claim 56, wherein Relative to ionomer I VDF SO3X The amount of these repeating units 3 is 0 mol% to 15 mol% of the total moles of the repeating units.

60. The method of claim 56, wherein Ionomer I VDF SO3X is a polymer composed of: (1) from 55 mol% to 95 mol% of repeating units derived from vinylidene fluoride; (2) from 5 mol% to 40 mol% of at least one -SO3X a group and is derived from at least one or more hydrolyzed repeating units of monomers 2; (3) from 0 mol% to 15 mol% of repeating units 3 derived from one or more hydrogenated or fluorinated monomers other than vinylidene fluoride, The above items are as described in Ionomer I VDF SO3X The total moles of repeating units are calculated.

61. The method of claim 60, wherein The repeating units derived from vinylidene fluoride are as described in Ionomer I VDF SO3X The total moles of the repeating units are from 70 mol % to 92 mol %.

62. The method of claim 60, wherein: Includes at least one -SO3X a and derived from at least one or more hydrolyzed repeating units of monomers 2 according to the ionomer 1 VDF SO3X The total molar amount of the repeating units is from 8 mol% to 30 mol%.

63. The method of claim 60, wherein: The repeating units 3 derived from one or more hydrogenated monomers or fluorinated monomers other than vinylidene fluoride are as described in the ionomer 1. VDF SO3X The total moles of the repeating units are from 0 mol % to 10 mol %.

64. The method of any one of claims 17 to 19, wherein Relative to ionomer I X The total weight of the ionizable groups in the ionomer I X The amount in the range is at least 0.55 meq / g, and / or at most 3.50 meq / g.

65. The method of claim 64, wherein Relative to ionomer I X The total weight of the ionizable groups in the ionomer I X The amount in the range is at least 0.65 meq / g.

66. The method of claim 64, wherein Relative to ionomer I X The total weight of the ionizable groups in the ionomer I X The amount in the range is at least 0.75 meq / g.

67. The method of claim 64, wherein Relative to ionomer I X The total weight of the ionizable groups in the ionomer I X The amount in is at most 3.20 meq / g.

68. The method of claim 64, wherein Relative to ionomer I X The total weight of the ionizable groups in the ionomer I X The amount in the range is at most 2.50 meq / g.

69. The method of any one of claims 17 to 19, wherein The material P consists of particles consisting of hollow agglomerates, the average particle size of which is at least 3 μm and / or at most 100 μm; and / or the material P consists of particles present in agglomerates of elementary particles, the average diameter of which is at least 30 nm and / or at most 140 nm.

70. The method of claim 69, wherein The material P consists of particles composed of hollow agglomerates, the average particle size of these particles being at least 5 μm.

71. The method of claim 69, wherein The material P consists of particles composed of hollow agglomerates, the average particle size of these particles being at most 50 μm.

72. The method of claim 69, wherein The material P consists of particles composed of hollow agglomerates, the average particle size of these particles being at most 40 μm.

73. The method of claim 69, wherein Said material P is constituted by particles present in agglomerates of elementary particles, these particles having an average diameter of at least 50 nm.

74. The method of claim 69, wherein The material P consists of particles present in agglomerates of elementary particles, the average diameter of these particles being at most 120 nm.

75. The method of claim 69, wherein Said material P consists of particles present in agglomerates of elementary particles, the average diameter of these particles being at most 100 nm.

Images