# US 12,110,352 B2 · Vinylidene fluoride polymer dispersion

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- Number: US 12,110,352 B2
- Document ID: US12110352B2
- Status: Granted
- Kind: B2
- Application number: 17/311,034
- Filed: 2019-12-02
- Published: 2022-01-27
- Granted: 2024-10-08
- Earliest claimed: 2018-12-20
- Assignees: Solvay Specialty Polymers Italy S.P.A.
- Applicants: Solvay Specialty Polymers Italy S.P.A.
- Inventors: Serena Carella; Mirko Mazzola; Marco Avataneo; Andrea Vittorio Oriani; Emanuele Di Nicolo′
- Web page: https://patentgrep.com/patent/US12110352B2

## CPC

- C08F 214/22: Vinylidene fluoride
- C08F 214/225: {with non-fluorinated comonomers}
- C08F 2/22: Emulsion polymerisation
- C08F 2/38: Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation}
- C08F 14/22: Vinylidene fluoride
- C08F 214/28: Hexyfluoropropene
- C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
- C08F 220/20: of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate}
- C08J 3/12: Powdering or granulating
- C08K 3/36: Silica
- C09D 127/16: Homopolymers or copolymers of vinylidene fluoride
- H01G 11/30: characterised by their material
- H01G 11/38: Carbon pastes or blends; Binders or additives therein
- H01G 11/52: Separators
- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- H01M 50/426: Fluorocarbon polymers
- H01M 50/446: Composite material consisting of a mixture of organic and inorganic materials
- H01M 50/449: having a layered structure
- C08F 220/281: {and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate}
- C08F 2438/03: Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
- C08F 2810/40: taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
- Y02E 60/10: Energy storage using batteries
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention pertains to an aqueous dispersion of a vinylidene fluoride polymer having a high molecular weight and possessing a substantially linear structure, leading to reduced amount of gels/insoluble fractions, to a method for its preparation and to its use for the manufacture of electrochemical cell components, such as electrodes and/or composite separators or for the manufacture of membranes.

## Claims

### Claim 1

An aqueous dispersion [dispersion (D)] comprising particles of a vinylidene fluoride (VDF) polymer [polymer (A)] comprising recurring units derived from vinylidene fluoride (VDF) monomer, said polymer (A) comprising
(i) more than 85.0% moles of recurring units derived from VDF, with respect to the total number of recurring units of polymer (A);
(ii) sulphur-containing chain ends;
(iii) a weight averaged molecular weight (Mw) of at least 500 KDalton, when measured by GPC, using N,N-dimethylacetamide (DMA) as solvent, against monodisperse polystyrene standards;
wherein the relation between melt viscosity (MV) in KPoise determined at a shear rate of 100 sec−1, and at a temperature of 230° C., according to ASTM D3835, and Mw, expressed in KDalton, satisfies the following inequality:
0.025×Mw (KDalton)+13≤MV (KPoise)≤0.050×Mw (KDalton)+10.

### Claim 2 (depends on 1)

The dispersion (D) of claim 1, wherein polymer (A) is selected from the group consisting of:
polymers consisting essentially of recurring units derived from VDF, and recurring units derived from at least one monomer (MA) the hydrophilic (meth)acrylic monomer (MA) complies formula:
wherein each of R1, R2, equal or different from each other, is independently a hydrogen atom or a C1-C3 hydrocarbon group, and R3 is hydrogen and Ron is a hydroxyl group or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group; and
polymers consisting essentially of recurring units derived from VDF, from HFP and from monomer (MA).

### Claim 3 (depends on 2)

The dispersion (D) of claim 2, wherein the monomer (MA) is selected from the group consisting of:
hydroxyethylacrylate (HEA) of formula:
2-hydroxypropyl acrylate (HPA) of either of formulae:
acrylic acid (AA) of formula:
and mixtures thereof.

### Claim 4 (depends on 1)

The dispersion (D) of claim 1, wherein polymer (A) comprises at least 0.1 moles of recurring units derived from said hydrophilic (meth)acrylic monomer (MA) and/or polymer (A) comprises at most 7.5% moles of recurring units derived from said hydrophilic (meth)acrylic monomer (MA).

### Claim 5 (depends on 1)

A method of making a dispersion (D) according to claim 1, said method comprising emulsion polymerization of VDF in an aqueous medium in the presence of an inorganic initiator and in the presence of a RAFT/MADIX agent of any general formulae (I) and (II):
wherein X is carbon or phosphorous; Ra is a monovalent organic group optionally substituted with one or more hydrophilic groups, Rb is a divalent organic group optionally substituted with one or more hydrophilic groups, and Z is any group that promotes reactivity of the thiocarbonyl group towards radical addition, wherein the molar ratio between the said RAFT/MADIX agent and the said initiator is of less than 0.050 mol/mol.

### Claim 6 (depends on 5)

The method of claim 5, wherein:
in formulae (I) and (II), Z is selected among —OH, —SH, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted alkylthio, optionally substituted arylalkylthio, dialkoxy- or diaryloxy-phosphinyl [—P(═O) (OR4)2], dialkyl- or diaryl-phosphinyl [—P(═O)R42], where R4 is selected from the group consisting of optionally substituted C1-C18 alkyl, optionally substituted C2-C18 alkenyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted alkaryl, optionally substituted acylamino, optionally substituted acylimino, optionally substituted amino, and a polymer chain selected from the group consisting of polyalkylene oxide polymers, and alkyl end capped derivatives thereof, wherein optional substituents for R4 and Z groups include epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and its salts), sulfonic acid (and its salts), alkoxy- or aryloxy-carbonyl, isocyanato, cyano, silyl, halo, and dialkylamino; and/or
wherein in formulae (I) and (II), X is a carbon atom and RAFT/MADIX agent is selected from formulae (I′) and (II′):
with Ra, Rb and Z being as above detailed.

### Claim 7 (depends on 6)

The method of claim 6, wherein said initiator is a persulfate radical initiator selected from the group consisting of sodium, potassium and ammonium persulfates, and wherein the amount of said initiator ranges from 0.001% to 20% by weight based on the weight of the aqueous medium.

### Claim 8 (depends on 6)

The method of claim 6 wherein:
the amount of RAFT/MADIX agent is such to provide for a molar ratio between said RAFT/MADIX agent and said initiator of at most 0.048 mol/mol; and/or of at least 0.005 mol/mol; and
the said RAFT/MADIX agent is O-ethyl S-(1-methoxycarbonyl ethyl) dithiocarbonate.

### Claim 9

A powder [powder (P)] comprising particles of a vinylidene fluoride (VDF) polymer [polymer (A)] comprising recurring units derived from vinylidene fluoride (VDF) monomer, said polymer (A) comprising:
(i) more than 85.0% moles of recurring units derived from VDF, with respect to the total number of recurring units of polymer (A);
(ii) sulphur-containing chain ends;
(iii) a weight averaged molecular weight (Mw) of at least 500 KDalton, when measured by GPC, using N,N-dimethylacetamide (DMA) as solvent, against monodisperse polystyrene standards;
wherein the relation between melt viscosity (MV) in KPoise determined at a shear rate of 100 sec−1, and at a temperature of 230° C., according to ASTM D3835, and Mw, expressed in KDalton, satisfies the following inequality:
0.025×Mw(KDalton)+13≤MV(KPoise)≤0.050×Mw(KDalton)+10,
wherein said particles of polymer (A) possess a primary particle average size of less than 1 μm, preferably a primary particles average size of above 20 nm and below 350 nm.

### Claim 10

A vinylidene fluoride (VDF) polymer [polymer (A)] comprising recurring units derived from vinylidene fluoride (VDF) monomer, said polymer (A) comprising:
(i) comprising more than 85.0% moles of recurring units derived from VDF, with respect to the total number of recurring units of polymer (A);
(ii) sulphur-containing chain ends;
(iii) a weight averaged molecular weight (Mw) of at least 500 KDalton, when measured by GPC, using N,N-dimethylacetamide (DMA) as solvent, against monodisperse polystyrene standards;
wherein the relation between melt viscosity (MV) in KPoise determined at a shear rate of 100 sec−1, and at a temperature of 230° C., according to ASTM D3835, and Mw, expressed in KDalton, satisfies the following inequality:
0.025×Mw(KDalton)+13≤MV(KPoise)≤0.050×Mw(KDalton)+10.

### Claim 11 (depends on 10)

A solvent-based electrode-forming composition comprising polymer (A) of claim 10, at least one polar organic solvent, a powdery electrode material and, optionally, an electro-conductivity-imparting additive and/or aviscosity modifying agent.

### Claim 12 (depends on 11)

The solvent-based electrode-forming composition of claim 11, wherein the polar organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, N,N-dimethylacetamide, N,N-dimethylsulfoxide, hexamethylphosphonamide, dioxane, tetrahydrofuran, tetramethylurea, triethylphosphate, trimethylphosphate, and any combination of one or more thereof.

### Claim 13 (depends on 1)

An aqueous electrode-forming composition comprising the dispersion (D) according to claim 1, a powdery electrode material, and, optionally an electroconductivity-imparting additive and/or a viscosity modifying agent.

### Claim 14 (depends on 1)

An aqueous coating composition [composition (AC)] comprising dispersion (D) according to claim 1, at least one non-electroactive inorganic filler material and, optionally, one or more than one additional additive.

### Claim 15 (depends on 14)

The composition (AC) of claim 14, wherein the non-electroactive inorganic filler material is selected from the group consisting of natural and synthetic silicas, zeolites, aluminas, titanias, metal carbonates, zirconias, silicon phosphates and silicates.

### Claim 16 (depends on 14)

The composition (AC) according to claim 14, said composition (AC) being obtained by mixing:
(i) dispersion (D) in an amount of from 5 to 25% wt;
(ii) at least one non-electroactive inorganic filler material, in an amount of from 70 to 95% wt;
(iii) one or more than one additional additive, in an amount of 0 to 5% wt; and
optionally, adding water for adjusting solid contents in the range of 30 to 80% wt.

### Claim 17 (depends on 14)

A method for the manufacture of a composite separator, said method comprising the following steps:
(i) providing a porous substrate;
(ii) providing the composition (AC) of claim 14;
(iii) applying said composition (AC) onto at least one surface of said porous substrate to provide a coating composition layer; and
(iv) drying said coating composition layer at a temperature of at least 60° C., to provide said composite separator.

### Claim 18 (depends on 9)

A method for making a membrane comprising using the powder (P) of claim 9, said method comprising the steps of:
(i) preparing a solution [solution (SM)] comprising:
polymer (A);
optionally, at least one pore forming agent [agent (P)]; and
a polar organic solvent;
(ii) processing said solution (SM) into a film; and
(iii) immersing said film in a non-solvent bath.

### Claim 19 (depends on 10)

A method for making a membrane comprising using the polymer (A) of claim 10, said method comprising the steps of:
(i) preparing a solution [solution (SM)] comprising:
polymer (A);
optionally, at least one pore forming agent [agent (P)]; and
a polar organic solvent;
(ii) processing said solution (SM) into a film; and
(iii) immersing said film in a non-solvent bath.

### Claim 20 (depends on 10)

A membrane comprising the polymer (A) according to claim 10.