FIELD OF THE INVENTION

[0001] The invention relates to novel linear, semi-crystalline, functional fluoropolymers that have been obtained by copolymerizing a fluorinated vinylic monomer and one or more hydrophilic comonomers. The comonomer may optionally be bearing a halogen functionality. At most 10.0 weight percent of the comonomer units are present in the copolymer as single monomer units between two fluoromonomer units. The invention also relates to a process for forming the copolymer of the fluoromonomers/comonomers. The functional fluoropolymers provide enhanced properties compared to the fluoropolymer alone, such as increased adhesion and hydrophilic characteristics. The fluoropolymer of the invention may be used in applications benefiting from a functional fluoropolymer including as binders in electrode-forming compositions and separator compositions, or in forming hydrophilic membranes and hollow fibers.

BACKGROUND OF THE RELATED ART

[0002] Fluoropolymers are traditionally used for applications requiring special properties, such as low surface energy, high resistance to chemical attack, aging resistance, and electrochemical stability. However, these advantageous properties also make fluoropolymers difficult to work with and limits their applications. For example, the lack of functional groups on the fluoropolymers makes them difficult: to adhere to substrates, to facilitate cross-linking, to provide sites for subsequent chemical modification, to be wetted by water, and to add hydrophilic characteristics. There is a need for fluorinated polymers having modified properties, such as functional groups, which can augment their properties.

[0003] However it is difficult to add functional monomer units directly into the polymerizing polymer backbone, especially in a random manner, due to the aggressive nature of the fluorine- containing free radicals. Functionality has been added by several means, such as, by direct copolymerization of a functional monomer with the fluoromonomers, and by a post polymerization grafting mechanism, such as the grafting of maleic anhydride onto a polyvinylidene fluoride homopolymer or copolymer, as described in US 7,241,817, to form KYNAR ^® ADX resins available from Arkema Inc. WO 2013/110740 and US 7,351,498 further describe functionalization of a fluoropolymer by monomer grafting or by copolymerization.

[0004] US 5,415,958, discloses copolymerization of vinylidene fluoride with an unsaturated dibasic acid monoester polar monomer, to introduce carbonyl groups to the backbone of PVDF in order to improve its adhesion to different substrates.

[0005] US 8,337,725 discloses copolymerization of vinylidene fluoride with at least one hydrophilic (meth)acrylic monomer of formula:

wherein each of Rl, R2, R3, equal or different from each other, is independently a hydrogen atom or a C1-C3 hydrocarbon group, and R _OH is a hydrogen or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group.

[0006] There is a need to further improve the adhesion performance of fluorinated polymers.

[0007] The art is silent as to functional fluoropolymers obtained by copolymerizing a fluorinated vinylic monomer and hydrophilic comonomers that may optionally be bearing a halogen functionality, that allow for improved adhesion to a substrate, when compared to the non functional fluoropolymer, while maintaining good mechanical and thermal properties.

BRIEF SUMMARY OF THE INVENTION

[0008] The invention relates to a fluorinated copolymer comprising a vinylic monomer and a hydrophilic monomer .

[0009] The invention further relates to a formulation comprising the fluorinated copolymer in a solvent, and may further comprise activated carbon and metal particles selected from the group: lithium iron phosphate (LFP), lithium nickel manganese cobalt oxide (NMC), lithium-manganese- cobalt-oxide, lithium-nickel-cobalt-aluminum oxide, lithium-manganese oxide, and lithium- nickel-manganese spinel.

[0010] The invention further contemplates a process for preparing the fluorinated copolymer in an aqueous reaction medium, comprising: a) forming an aqueous emulsion comprising at least one initiator, a stabilizer, at least one fluoromonomer and a hydrophilic monomer, b) initiating copolymerization of said at least one fluoromonomer with said hydrophilic monomer with stirring, under heat and - pressure.

[0011] The invention further relates to articles formed from the fluorinated copolymer, which benefit from the special properties of the functional copolymer. These articles find uses in applications such as for: an electrode or separator for a battery or capacitor; a hydrophilic porous membrane or hollow fiber membrane; an article coated on at least one surface with said functional fluoropolymer, impregnation of woven and unwoven fibers, and a multi-layer construction wherein said functional fluoropolymer forms a tie layer between a fluoropolymer layer and a polymer layer that is incompatible with said fluoropolymer layer.

DETAILED DESCRIPTION

[0012] Fluoropolymers, particularly poly(vinylidene fluoride) (PVDF) and its copolymers find application as the binder in electrode articles used in lithium ion batteries. As the demand for greater battery performance intensifies, the need for reduction of the binder content in the electrodes has increased. To reduce the binder content, it is paramount to increase the performance of the binder material. The initial performance is determined by an adhesion test whereby a formulated electrode is subjected to a peel test. Improvements in this test translates to improved binding performance and the potential to reduce the overall binder loading, increasing active material loading and improving battery capacity. It has been shown that copolymers of fluorinated vinylic monomers with acid-functional comonomers lead to this type of adhesion performance improvement. These approaches have also suffered from low reaction productivity, and difficulty to supply sufficient quantities of material to a rapidly-growing market. Here, we present a new copolymer and process with vastly improved productivity (i.e. reduced time for polymerization).

[0013] The invention solves the above-cited problems by providing a fluorinated copolymer comprising a fluorinated vinylic monomer and a hydrophilic comonomer,

[0014] The fluorinated vinylic monomer is selected from the group comprising: vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), vinyl fluoride (VF), hexafluoroisobutylene (HFIB), perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-trifluoro-l-propene, 2-trifluoromethyl- 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, fluorinated vinyl ethers including perfluoromethyl ether (PMVE), perfluoroethylvinyl ether (PEVE), perfluoropropylvinyl ether (PPVE), perfluorobutylvinyl ether (PBVE), longer alkyl chain perfluorinated vinyl ethers, fluorinated dioxoles, partially- or per-fluorinated alpha olefins of C4 and higher, partially- or per fluorinated cyclic alkenes of C3 and higher, and combinations thereof.

[0015] The hydrophilic comonomer is selected from vinyl alkyl acids, vinyl phosphonates, functional acrylamides, carbonates, vinyl ethers, allyloxy compounds, and vinyl or allyl-double hydrophilic group monomers and combinations thereof.

[0016] The functional copolymer according to the invention is further characterized by the following embodiments.

[0017] According to one embodiment, the fluorinated copolymer comprises 0.01 to 10.0 wt% of one or more hydrophilic monomers and 90.0 to 99.99 wt% of fluorinated vinylic monomer.

[0018] According to one embodiment, the fluorinated copolymer comprises vinylidene fluoride and one or more hydrophilic monomer.

[0019] According to one embodiment, the fluorinated copolymer comprises vinylidene fluoride and one or more hydrophilic monomer, wherein said hydrophilic monomer contains at least one halogen atom on at least one of the vinyl carbons.

[0020] According to one embodiment, said hydrophilic monomer contains at least one fluorine atom on at least one of the vinyl carbons.

[0021] The invention further relates to a formulation comprising the fluorinated copolymer in a solvent. The solvent is preferably chosen from: n-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), triethylphosphite (TEP), acetone, tetrahydrofuran, methyl ethylketone (MEK), methyl isobutyl ketone (MiBK), ethyl acetate (EA), butyl acetate (BA), dimethyl carbonate (DMC), diethyl carbonate (DEC) or methyl ethyl carbonate (MEC).

[0022] According to one embodiment, the formulation further comprises activated carbon and lithium salt particles in suspension in said solvent. The lithium salt particles are selected from the group: lithium iron phosphate (LFP), lithium nickel manganese cobalt oxide (NMC), Lithium cobalt oxide (LCO), lithium manganese oxide (LMO), lithium nickel-cobalt-aluminum oxide (NCA), and lithium-nickel-manganese oxide (LNMO). Such formulation is particularly suitable for forming a battery electrode film, notably a positive electrode for a lithium ion battery. The invention encompasses a battery comprising the fluorinated copolymer described herein.

[0023] The invention further contemplates a process for preparing the fluorinated copolymer in an aqueous reaction medium, comprising:

a) forming an aqueous emulsion comprising at least one initiator, a stabilizer, at least one fluorinated vinylic monomer, and a hydrophilic monomer, as defined above,

b) initiating copolymerization of said at least one fluorinated vinylic monomer with said hydrophilic monomer with stirring, under heat and pressure.

[0024] A polymerization reaction in accordance with the present invention may be carried out by charging a reactor with water (preferably deionized water), at least one fluorinated vinylic monomer, at least one hydrophilic monomer as defined above and optionally, one or more of a surfactant, a chain-transfer agent and/or an antifoulant. Air may be purged from the reactor prior to the introduction of the monomers. Water is added to the reactor before bringing the reactor to the desired starting temperature, but the other materials may be added before or after bringing the reactor to temperature. At least one radical initiator is added to start and maintain the polymerization reaction. Additional monomer may be optionally added to replenish monomer that is consumed, and the other materials may be optionally added during the course of the polymerization to maintain the reaction and control the final product properties.

[0025]“Copolymer” is used to mean a polymer having two or more different monomer units. “Polymer” is used to mean both homopolymer and copolymers. Polymers may be straight chain, branched, star comb, block, or any other structure. The polymers may be homogeneous, heterogeneous, and may have a gradient distribution of co-monomer units. Ah references cited are incorporated herein by reference. As used herein, unless otherwise described, percent shah mean weight percent. Unless otherwise stated, molecular weight is a weight average molecular weight as measured by GPC, using a polymethyl methacrylate standard. In cases where the polymer contains some cross-linking, and GPC cannot be applied due to an insoluble polymer fraction, soluble fraction/ gel fraction or soluble faction molecular weight after extraction from gel is used. Crystallinity and melting temperature are measure by DSC as described in ASTM D3418 at heating rate of 10 C/min. Melt viscosity is measured in accordance with ASTM D3835 at 230°C expressed in k Poise @ 100 Sec ^A (-l). Hydrophilic Monomer

[0026] The hydrophilic comonomers used in combination with the one or more fluoromonomers include, but are not limited to one or more of the following, with mixtures of more than one monomer in a particular class, and two or more monomers from different classes below, being blended together to form a terpolymer:

[0027] A) Vinyl alkyl acids,

having as a comonomer (Ml):

Wherein Rl, R2, and R3 is a hydrogen or a halogen (F, Cl, Br, I).

Wherein R4 is a Cl to C 16 linear, branched, aryl, or cycloalkyl group, a Cl to C 16 fluorinated linear, branched, aryl or cycloalkyl group, an oligomer of hexfluoropropylene oxide or an oligomer of tetrafluoroethylene oxide.

Wherein R5 is carboxylic acid (C(O)OH), alkali metal carboxylate salt (COO M ⁺ ), ammonium carboxylate salt (COO NH ₄ ⁺ ), alkylammonium carboxylate salt (COO N(Alk) ₄ ⁺ ), alcohol (OH), amide (C(0)NH ₂ ), dialkyl amide (C(0)NAlk ₂ ), sulfonic acid (S(0)(0)0H), alkali metal sulfonate salt (S(0)(0)0 M ⁺ ), ammonium sulfonate salt (S(0)(0)0 NH ₄ ⁺ ), alkylammonium sulfonate salt (S(0)(0)0 N(Alk) ₄ ⁺ ).

[0028] B) Vinyl alkyl acids,

having the formula M2 below:

Wherein: Rl, R2, and R3 is a hydrogen or a halogen (F, Cl, Br, I);

Wherein: R4 and R5 are, separately, hydrogen, a Cl to C16 linear alkyl, branched alkyl, aryl, or cycloalkyl group, a Cl to Cl 6 fluorinated linear alkyl, branched alkyl, aryl or cycloalkyl group, an oligomer of hexfluoropropylene oxide or an oligomer of tetrafluoroethylene oxide, alkali metal ion (Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ), ammonium ion (NH ₄ ⁺ ), or alkylammonium (NAlk ₄ ⁺ ) [0029] C) Functional acrylamides,

having as a comonomer (M3):

Wherein: Rl, R2, and R3 is a hydrogen or a halogen (F, Cl, Br, I).

Wherein: R4 and R6, separately are a hydrogen, Cl to C16 linear, branched, aryl, or cycloalkyl group, a Cl to C16 fluorinated linear, branched, aryl or cycloalkyl group, an oligomer of hexafluoropropylene oxide or an oligomer of tetrafluoroethylene oxide.

Wherein: R5 and R7, separately are carboxylic acid (C(O)OH), alkali metal carboxylate salt (COO M ⁺ ), ammonium carboxylate salt (COO NH ₄ ⁺ ), alkylammonium carboxylate salt (COO N(Alk) ₄ ⁺ ), alcohol (OH), amide (C(0)NH ₂ ), dialkyl amide (C(0)NAlk ₂ ), sulfonic acid (S(0)(0)0H), alkali metal sulfonate salt (S(0)(0)0 M ⁺ ), ammonium sulfonate salt (S(0)(0)0 NH ₄ ⁺ ), alkylammonium sulfonate salt (S(0)(0)0 N(Alk) ₄ ⁺ ), ketone (C(O)), or acetylacetonate (C(0)-CH2-C(0)), or phosphonate (P(0)(0H)2), alkali metal or ammonium phosphonate

[0030] D) Carbonates,

containing the comonomer M4:

Wherein: Rl, R2, and R3 is a hydrogen or a halogen (F, Cl, Br, I).

Wherein: R4 is a bond, a Cl to C16 linear alkyl, branched alkyl, aryl, or cycloalkyl group, a Cl to C16 fluorinated linear alkyl, branched alkyl, aryl or cycloalkyl group.

Wherein: R5 is Cl to C16 cycloalkyl group, a Cl to C 16 fluorinated cycloalkyl group, containing a carbonate group as part of the cyclic structure.

[0031] E) Vinyl Ethers, having as a comonomer (M5):

Wherein: Rl, R2, and R3 is a hydrogen or a halogen (F, Cl, Br, I).

Wherein: R4 is a Cl to C 16 linear, branched, aryl, or cycloalkyl group, a Cl to C 16 fluorinated linear, branched, aryl or cycloalkyl group, an oligomer of hexfluoropropylene oxide or an oligomer of tetrafluoroethylene oxide.

Wherein: R5 is carboxylic acid (C(O)OH), alkali metal carboxylate salt (COO M ⁺ ), ammonium carboxylate salt (COO NH ₄ ⁺ ), alkylammonium carboxylate salt (COO N(Alk) ₄ ⁺ ), alcohol (OH), amide (C(0)NH ₂ ), dialkyl amide (C(0)NAlk ₂ ), sulfonic acid (S(0)(0)0H), alkali metal sulfonate salt (S(0)(0)0 M ⁺ ), ammonium sulfonate salt (S(0)(0)0 NH ₄ ⁺ ), alkylammonium sulfonate salt (S(0)(0)0 N(Alk) ₄ ⁺ ), ketone (C(O)), acetylacetonate (C(0)-CH2-C(0))

[0032] F) Allyloxy compounds having as a comonomer (M6):

Wherein: Rl, R2, and R3 is a hydrogen or a halogen (F, Cl, Br, I).

Wherein: R4 is CH ₂ or CF ₂ ;

Wherein: R5 is a Cl to C 16 linear, branched, aryl, or cycloalkyl group, a Cl to C 16 fluorinated linear, branched, aryl or cycloalkyl group, an oligomer of hexafluoropropylene oxide or an oligomer of tetrafluoroethylene oxide.

Wherein: R6 is carboxylic acid (C(O)OH), alkali metal carboxylate salt (COO M ⁺ ), ammonium carboxylate salt (COO NH ₄ ⁺ ), alkylammonium carboxylate salt (COO N(Alk) ₄ ⁺ ), alcohol (OH), amide (C(0)NH ₂ ), dialkyl amide (C(0)NAlk ₂ ), sulfonic acid (S(0)(0)0H), alkali metal sulfonate salt (S(0)(0)0 M ⁺ ), ammonium sulfonate salt (S(0)(0)0 NH ₄ ⁺ ), alkylammonium sulfonate salt (S(0)(0)0 N(Alk) ₄ ⁺ ), ketone (C(O)), or acetylacetonate (C(0)-CH2-C(0)), or phosphonate (P(0)(0H)2), alkali metal or ammonium phosphonate.

[0033] G) Multi-hydrophilic group comonomers

[0034] Monomers having two or more hydrophilic groups are also contemplated by the invention. These include, but are not limited to itaconic acid, maleic acid, glutaconic acid, fumaric acid, and the anhydrides, alkali metal salts, ammonium, and mono-, di-, tri-, and tetraalkylammonium salts thereof.

[0035] The hydrophilic comonomers may be used in the reactor in an amount, for example, of from about 0.01 to about 15 weight percent based on total monomer. Preferably they are used in an amount from about 0.01 to about 5 weight percent based on total monomer. In various embodiments, the total amount of hydrophilic monomer(s) is at least 0.01, at least 0.05, at least 0.1, at least 1.0 or at least 2.0 weight percent based on total monomer. In other embodiments, the total amount of hydrophilic monomer does not exceed 13.0, 10.0, 9.0, 7.0, 6.0, 5.0 weight percent based on total monomer. The hydrophilic comonomer may be used in solution such as in aqueous solution for convenient handling.

[0036] The polymer may comprise from 0.01 to 15.0 wt% of said hydrophilic monomers and 85.0 to 99.99wt% of fluorinated vinylic monomer.

Surfactants

[0037] The surfactant used in the polymerization can be any surfactant known in the art to be useful in PVDF emulsion polymerization, including perfluorinated, partially fluorinated, and non- fluorinated surfactants. In a preferred embodiment, the PVDF emulsion of the present disclosure can be fluorosurfactant free, with no fluoro surfactants being used in any part of the polymerization. Non-fluorinated surfactants useful in the PVDF polymerization could be both ionic and non-ionic in nature including, but are not limited to, 3-allyloxy-2-hydroxy-l-propane sulfonic acid salt, polyvinylphosphonic acid, polyacrylic acids, polyvinyl sulfonic acid, and salts thereof, polyethylene glycol and/or polypropylene glycol and the block copolymers thereof, alkyl phosphonates and siloxane-based surfactants

[0038] Surfactants can also be used in combination with the hydrophilic comonomer to provide further stability to the polymer emulsion. Preferred surfactants are non-fluorinated hydrocarbon surfactants, siloxane surfactants or a combination thereof. For example a hydrophilic (meth)acrylic comonomer can be used in combination with sodium dodecyl benzene sulfonate (SDDBS), sodium octyl sulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, and sodium laureth sulfate, among others. In certain embodiments of the invention, no fluorosurfactant is present in the aqueous emulsion and/or no fluorosurfactant is introduced during copolymerization of the fluorinated vinylic monomer with the hydrophilic (meth) acrylic comonomer. In one embodiment, the stabilizer is a polyelectrolyte. In another embodiment, the stabilizer of the polymer emulsion is a functionalized cellulose.

Initiators

[0039] The term "initiator" and the expressions "radical initiator" and "free radical initiator" refer to a chemical that is capable of providing a source of free radicals, either induced spontaneously, or by exposure to heat or light. Examples of suitable initiators include peroxides, peroxydicarbonates and azo compounds. “Initiators” also includes redox systems useful in providing a source of free radicals. The term "radical" and the expression "free radical" refer to a chemical species that contains at least one unpaired electron.

[0040] The radical initiator is added to the reaction mixture in an amount sufficient to initiate and maintain the polymerization reaction at a desired reaction rate. The order of addition may vary according to the desired process and latex emulsion characteristics.

[0041] The radical initiator may comprise a persulfate salt, such as sodium persulfate, potassium persulfate, or ammonium persulfate. The amount of persulfate salt added to the reaction mixture (based upon the total weight of monomer added to the reaction mixture) may, for example, be from about 0.002 to about 1.0 weight percent.

[0042] The radical initiator may comprise an organic peroxide such as an alkyl, dialkyl, or diacyl peroxide, peroxydicarbonates, and peroxy esters or mixtures thereof. A preferred dialkyl peroxide is di-tert-butylperoxide (DTBP), which may be added to the reaction mixture in an amount from about 0.01 to about 5 weight percent on total monomer, and is preferably added in an amount from about 0.05 to about 2.5 weight percent on total monomer. Preferred peroxydicarbonate initiators are di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate, which may be added to the reaction mixture in an amount from about 0.5 to about 2.5 weight percent on total monomer. Peroxy ester initiators include tert-amyl peroxypivalate, tertbutyl peroxypivalate, and succinic acid peroxide.

[0043] The radical initiator may comprise an azo initiator, such as 2,2'- azobis(2 methyl- propionamidine)dihydrochloride.

[0044] The radical initiator may comprise a redox system. By "redox system" is meant a system comprising an oxidizing agent, a reducing agent and optionally, a promoter as an electron transfer medium. Oxidizing agents include, for example, persulfate salts; peroxides, such as hydrogen peroxide; hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide; and oxidizing metal salts such as, for example, ferric sulfate. Reducing agents include, for example, sodium formaldehyde sulfoxylate, sodium and potassium sulfite, ascorbic acid, bisulfite, metabisulfite, and reduced metal salts. The promoter is a component of the redox system which, in different oxidation states, is capable of reacting with both the oxidant and the reducing agent, thereby accelerating the overall reaction. Promoters include, for example, transition metal salts such as ferrous sulfate. In redox systems, the oxidizing agent and the reducing agent may be utilized in an amount from about 0.01 to about 0.5 weight percent on total monomer. The optional promoter may be utilized in an amount from about 0.005 to about 0.025 weight percent on total monomer. Redox systems are described in G.S. Misra and U.D.N. Bajpai, Prog. Polym. Sci., 1982, 8(1-2), pp. 61-131.

Chain-Transfer Agents

[0045] Chain-transfer agents are added to the polymerization to regulate the molecular weight of the product. They may be added to a polymerization in a single portion at the beginning of the reaction, or incrementally or continuously throughout the reaction. The amount and mode of addition of chain-transfer agent depend on the activity of the particular chain transfer agent employed, and on the desired molecular weight of the polymer product. The amount of chain- transfer agent added to the polymerization reaction is preferably from about 0.05 to about 5 weight percent, more preferably from about 0.1 to about 2 weight percent based on the total weight of monomer added to the reaction mixture.

[0046] Oxygenated compounds such as alcohols, carbonates, ketones, esters, and ethers may serve as chain-transfer agents. Examples of oxygenated compounds useful as chain-transfer agents include isopropyl alcohol, as described in U.S. Patent 4,360,652. Other classes of compounds which may serve as chain-transfer agents in the polymerization of halogen-containing monomers include, for example, halocarbons and hydrohalocarbons, such as chlorocarbons. Alkanes such as ethane and propane may also function as chain-transfer agents. Buffering Agent

[0047] The polymerization reaction mixture may optionally contain a buffering agent to maintain a controlled pH throughout the polymerization reaction. The pH is preferably controlled within the range of from about 4 to about 8, to minimize undesirable color development in the product.

[0048] Buffering agents may comprise an organic or inorganic acid or alkali metal salt thereof, or base or salt of such organic or inorganic acid, that has at least one pK _a value and/or pK _b value in the range of from about 4 to about 10, preferably from about 4.5 to about 9.5. Preferred buffering agents in the practice of the invention include, for example, phosphate buffers and acetate buffers. A "phosphate buffer" is a salt or a mixture of salts of phosphoric acid. An "acetate buffer" is a salt of acetic acid.

[0049] Buffering agents are preferably employed where potassium persulfate is employed as the radical initiator. A preferred buffering agent for use with persulfate radical initiators is sodium acetate. A preferred amount of sodium acetate buffer is from about 50 wt.% to about 150 wt.%, based on the weight of persulfate initiator added to the reaction. In one preferred embodiment, the initiator feed comprises approximately equal weights of potassium persulfate and sodium acetate in aqueous solution.

Antifoulant

[0050] The addition of a paraffin wax or hydrocarbon oil to the reaction serves as an antifoulant to minimize or prevent polymer adhesions to the reactor components. Any long chain saturated hydrocarbon wax or oil can perform this function. The amount of oil or wax added to the reactor is an amount that serves to minimize the formation of polymer adhesions on the reactor components. The amount is generally proportional to the interior surface area of the reactor and may vary from about 1 to about 40 mg per square centimeter of reactor interior surface area. The amount of paraffin wax or hydrocarbon oil is preferably about 5 mg/cm ² of the reactor interior surface area.

Co-Polymerization Conditions

[0051] The temperature used for polymerization may vary, for example, from 20-130 degrees Celsius, depending on the initiator system chosen. The polymerization temperature is preferably from 35-130 degrees Celsius, and most preferably from 70-125 degrees Celsius.

[0052] The pressure used for polymerization may vary from 280-20,000 kPa, depending on the capabilities of the reaction equipment, the initiator system chosen, and the monomer selection. The polymerization pressure is preferably from 2,000-11,000 kPa, and most preferably from 2,750-6,900 kPa.

[0053] The polymerization occurs under stirring or other agitation. The stirring/agitation may be constant, or may be varied to optimize process conditions during the course of the polymerization. In one embodiment, both multiple stirring speeds and multiple temperatures are used for controlling the reaction.

[0054] According to one embodiment of the process of the invention, a pressurized polymerization reactor equipped with a stirrer and heat control means is charged with water, preferably deionized water, one or more halogenated monomers (1) and at least one fluorinated vinylic monomer. The mixture may optionally contain one or more of a surfactant, a buffering agent, an antifoulant or a chain-transfer agent for molecular weight regulation of the polymer product.

[0055] Prior to introduction of the monomer or monomers, air is preferably removed from the reactor in order to obtain an oxygen-free environment for the polymerization reaction.

[0056] The order in which the polymerization components are assembled may be varied, although it is generally preferred that at least a portion of the hydrophilic monomer is present in the aqueous reaction medium prior to the initiation of the polymerization of the fluorinated vinylic monomer. An additional amount of hydrophilic monomer may be fed to the reactor during the reaction.

[0057] In one embodiment, water, initiator, hydrophilic monomer and optionally surfactant, antifoulant, chain transfer agent and/or buffer are charged to the reactor, and the reactor heated to the desired reaction temperature. The fluorinated vinylic monomer(s) is (are) then fed into the reactor, preferably at a rate which provides an essentially constant pressure.

[0058] Alternatively the fluorinated vinylic monomer, hydrophilic monomer and initiator can be fed to the reactor, along with one or more of the optional ingredients. Other variations for fluoropolymer copolymerization processes are contemplated, as known in the art.

[0059] The monomer feed is terminated when the desired weight of monomer has been fed to the reactor. Additional radical initiator is optionally added, and the reaction is allowed to react out for a suitable amount of time. The reactor pressure drops as the monomer within the reactor is consumed.

[0060] Upon completion of the copolymerization reaction, the reactor is brought to ambient temperature and the residual unreacted monomer is vented to atmospheric pressure. The aqueous reaction medium containing the copolymer is then recovered from the reactor as a latex. The latex consists of a stable mixture of the reaction components, i.e., water, hydrophilic monomer, initiator (and/or decomposition products of the initiator) and copolymer solids.

[0061] Generally, the latex contains from about 10 to about 50 weight percent copolymer solids. The polymer in the latex may be in the form of small particles having a size range of from about 30 nm to about 800 nm.

Product Handling

[0062] The product of the copolymerization is a latex which can be used in that form, usually after filtration of solid byproducts from the polymerization process, or which can be coagulated to isolate the solids, which may then be washed and dried. For use in latex form, the latex can be stabilized by the addition of a surfactant, which may be the same as or different from the surfactant present during polymerization (if any). This later added surfactant may, for example, be an ionic or non-ionic surfactant. In one embodiment of the invention, no fluorosurfactant is added to the latex. For solid product, the latex may be coagulated mechanically or by the addition of salts or acids, and then isolated by well-known means such as by filtration. Once isolated, solid product can be purified by washing or other techniques, and it may be dried for use as a powder, which can be further processed into granules, pellets or the like.

[0063] In one embodiment, the functional copolymer according to the invention is applied to a substrate, as a latex in water or as a solvent solution, the solvent being chosen among those listed above. Optionally, a primer layer can be applied to the substrate, before the layer of functional copolymer.

[0064] In one embodiment, said substrate is porous, for example a porous membrane.

EXAMPLES

[0065] Determination of Comonomer Incorporation by 19F NMR.

[0066] The degree of comonomer incorporation was determined by 19F NMR. ¹⁹ F and ' H NMR spectra were acquired on Bruker AV III 500 (11.7 T) with a 5 mm TXO probe, at 80 °C. Each sample was dissolved in DMSO-dr, at 80 °C for at least 24h for analysis. The peak appearing at 93.5ppm corresponding to -CF2- groups in alpha position to incorporated comonomer units was integrated in relation to the total integration of all 19F signals for the material. [— CH ₂ -CF ₂ -CH ₂ - CH(R)-CH ₂ -CF _2— (where R represents a bond or spacer group with hydrophilic functionality)] The ratio of the values determined from these integration was taken as the incorporated amount of comonomer. Using this methodology, it was determined a minimum detectable quantity of incorporation was lOOppm. The measurement of the amount of Monomer of ppm is in weight by weight.

[0067] Example 1: A solution of sodium undecylenate (NaUDA) was prepared by adding 2.0g of undecylenic acid (UDA) to a solution of 192. Og deionized water and 6.0g of 1 molar sodium hydroxide (NaOH) with vigorous agitation.

[0068] To a two liter autoclave were added lOOOg of deionized water, l.6g of low molecular weight poly(acrylic acid) (BASF CP-10S), and 50g of the NaUDA solution . The autoclave was deoxygenated by admission of 60psi nitrogen and venting, repeating this procedure two more times. Agitation was started and the autoclave was heated to 83C and pressurized to 650psi with vinylidene fluoride. A feed of 2.0wt% each potassium persulfate (KPS) and sodium acetate was started at 5.0mL/min. Upon start of pressure drop, an additional feed of NaUDA was started at l.OmL/min and KPS feed reduced to l.OmL/min. and pressure was maintained by additional VDF feed. Feeds were continued in this fashion, increasing NaUDA feed rate to moderate instantaneous VDF feed demand to maintain a range of 500- lOOOg/hr. NaUDA feed was increased in this fashion up to 5.OmL/min. All feeds were continued until a total of 700g of VDF had been fed to the reactor. Monomer feeds were stopped and the pressure was allowed to autogenously decrease for 10 minutes at which point the reactor was vented to atmospheric pressure and cooled to room temperature. Latex was discharged from the reactor and dried in a convection oven overnight.

[0069] Example 2: The procedure as outlined in Example 1 was followed, except that the NaUDA solution concentration was increased to 3.0wt% by using 6.0g of UDA, 18. Og of NaOH and 176. Og of deionized water and the KPS solution concentration was increased to 4.0wt%.

[0070] Example 3: A solution of sodium vinylphosphonate (NaVPA) was prepared by adding 6.65g of vinylphosphonic acid (VPA) to a solution of 123. lg 0.5N sodium hydroxide solution and 29.8g deionized water with vigorous agitation. [0071] To a two liter autoclave were added 900g of deionized water, 2.3g of low molecular weight poly(acrylic acid) (BASF CP-10S), and 25g of the NaVPA solution. The autoclave was deoxygenated by admission of 60psi nitrogen and venting, repeating this procedure two more times. Agitation was started and the autoclave was heated to 83C and pressurized to 650psi with vinylidene fluoride. A feed of 4.0wt% each potassium persulfate (KPS) was started at 5.0mL/min. Upon start of pressure drop, an additional feed of NaVPA was started at l.OmL/min and KPS feed reduced to l.OmL/min. and pressure was maintained by additional VDF feed. Feeds were continued in this fashion, increasing NaVPA feed rate to moderate instantaneous VDF feed demand to maintain a range of 500-l000g/hr. NaVPA feed was increased in this fashion up to 5.0mL/min. All feeds were continued until a total of 700g of VDF had been fed to the reactor. Monomer feeds were stopped and the pressure was allowed to autogenously decrease for 10 minutes at which point the reactor was vented to atmospheric pressure and cooled to room temperature. Latex was discharged from the reactor and dried in a convection oven overnight.

[0072] Example 4: The procedure as outlined in Example 3 was followed, except that the KPS solution concentration was decreased to 2.5wt%. Melting point (C, DSC 2 ^nd heat) was determined to be 161.8. Enthalpy of crystallization was 48.0 J/g

[0073] Example 5: Example (acrylamide): To a two liter autoclave would be added 900g of deionized water, 2.3g of low molecular weight poly(acrylic acid) (BASF CP-10S), and 25g of a l.0wt% aqueous solution of acrylamide. The autoclave would be deoxygenated by admission of 60psi nitrogen and venting, repeating this procedure two more times. Agitation would be started and the autoclave would be heated to 83C and pressurized to 650psi with vinylidene fluoride. A feed of 4.0wt% each potassium persulfate (KPS) would be started at 5.0mL/min. Upon start of pressure drop, an additional feed of acrylamide would be started at l.OmL/min and KPS feed reduced to l.OmL/min. and pressure maintained by additional VDF feed. Feeds would be continued in this fashion, increasing acrylamide feed rate to moderate instantaneous VDF feed demand to maintain a range of 500-l000g/hr. Acrylamide feed would be increased in this fashion up to 5.0mL/min. All feeds would be continued until a total of 700g of VDF had been fed to the reactor. Monomer feeds would be stopped and the pressure would be allowed to autogenously decrease for 10 minutes at which point the reactor would be vented to atmospheric pressure and cooled to room temperature. Latex would be discharged from the reactor and dried in a convection oven overnight. [0074] Example 6: Example (vinylene carbonate): To a two liter autoclave would be added 900g of deionized water, 2.3g of low molecular weight poly(acrylic acid) (BASF CP-10S), and 25g of a l.0wt% aqueous solution of vinylene carbonate. The autoclave would be deoxygenated by admission of 60psi nitrogen and venting, repeating this procedure two more times. Agitation would be started and the autoclave would be heated to 83C and pressurized to 650psi with vinylidene fluoride. A feed of 4.0wt% each potassium persulfate (KPS) would be started at 5.0mL/min. Upon start of pressure drop, an additional feed of vinylene carbonate would be started at l.OmL/min and KPS feed reduced to l.OmL/min. and pressure maintained by additional VDF feed. Feeds would be continued in this fashion, increasing vinylene carbonate feed rate to moderate instantaneous VDF feed demand to maintain a range of 500-l000g/hr. vinylene carbonate feed would be increased in this fashion up to 5.0mL/min. All feeds would be continued until a total of 700g of VDF had been fed to the reactor. Monomer feeds would be stopped and the pressure would be allowed to autogenously decrease for 10 minutes at which point the reactor would be vented to atmospheric pressure and cooled to room temperature. Latex would be discharged from the reactor and dried in a convection oven overnight.

[0075] Example 7: Example (vinylene carbonate): To a two liter autoclave would be added 900g of deionized water, 2.3g of low molecular weight poly(acrylic acid) (BASF CP-10S), and 25g of a l.0wt% aqueous solution of carboxyethyl vinyl ether. The autoclave would be deoxygenated by admission of 60psi nitrogen and venting, repeating this procedure two more times. Agitation would be started and the autoclave would be heated to 83C and pressurized to 650psi with vinylidene fluoride. A feed of 4.0wt% each potassium persulfate (KPS) would be started at 5.0mL/min. Upon start of pressure drop, an additional feed of carboxyethyl vinyl ether would be started at 1.OmL/min and KPS feed reduced to l.OmL/min. and pressure maintained by additional VDF feed. Feeds would be continued in this fashion, increasing carboxyethyl vinyl ether feed rate to moderate instantaneous VDF feed demand to maintain a range of 500-l000g/hr. carboxyethyl vinyl ether feed would be increased in this fashion up to 5. OmL/min. All feeds would be continued until a total of 700g of VDF had been fed to the reactor. Monomer feeds would be stopped and the pressure would be allowed to autogenously decrease for 10 minutes at which point the reactor would be vented to atmospheric pressure and cooled to room temperature. Latex would be discharged from the reactor and dried in a convection oven overnight. [0076] Example 8: A solution of allyloxyethanol (AOE) was prepared by adding 6.0g of AOE to 294.0g deionized water with vigorous agitation.

[0077] To a two liter autoclave were added 900g of deionized water, 2.3g of low molecular weight poly(acrylic acid) (BASF CP-10S), and lOg of the AOE solution. The autoclave was deoxygenated by admission of 60psi nitrogen and venting, repeating this procedure two more times. Agitation was started and the autoclave was heated to 83C and pressurized to 650psi with vinylidene fluoride. A feed of 4.0wt% each potassium persulfate (KPS) was started at 5.0mL/min. Upon start of pressure drop, an additional feed of AOE was started at l.OmL/min and KPS feed reduced to l.OmL/min. and pressure was maintained by additional VDF feed. Feeds were continued in this fashion, increasing AOE feed rate to moderate instantaneous VDF feed demand to maintain a range of 500-l000g/hr. AOE feed was increased in this fashion up to 5.0mL/min. All feeds were continued until a total of 700g of VDF had been fed to the reactor. Monomer feeds were stopped and the pressure was allowed to autogenously decrease for 10 minutes at which point the reactor was vented to atmospheric pressure and cooled to room temperature. Latex was discharged from the reactor and dried in a convection oven overnight.

[0078] Example 9: The procedure as outlined in Example 3 was followed, except that the AOE solution concentration was increased to 4.0wt% (12. Og AOE + 288.0g deionized water).

[0079] Example 10: A solution of allyloxypropane diol (AOPD) was prepared by adding 12. Og of AOPD to 288.0g deionized water with vigorous agitation.

[0080] To a two liter autoclave were added 900g of deionized water, 2.3g of low molecular weight poly(acrylic acid) (BASF CP-10S), and lOg of the AOPD solution. The autoclave was deoxygenated by admission of 60psi nitrogen and venting, repeating this procedure two more times. Agitation was started and the autoclave was heated to 83C and pressurized to 650psi with vinylidene fluoride. A feed of 4.0wt% each potassium persulfate (KPS) was started at 5.0mL/min. Upon start of pressure drop, an additional feed of AOPD was started at l.OmL/min and KPS feed reduced to l.OmL/min. and pressure was maintained by additional VDF feed. Feeds were continued in this fashion, increasing AOPD feed rate to moderate instantaneous VDF feed demand to maintain a range of 500-l000g/hr. AOPD feed was increased in this fashion up to 5.0mL/min. All feeds were continued until a total of 700g of VDF had been fed to the reactor. Monomer feeds were stopped and the pressure was allowed to autogenously decrease for 10 minutes at which point the reactor was vented to atmospheric pressure and cooled to room temperature. Latex was discharged from the reactor and dried in a convection oven overnight.

[0081] Example 11: The procedure as outlined in Example 10 was followed, except that the KPS solution concentration was decreased to 2.5wt%.

[0082] Example 12: A solution (AA/AOE) of acrylic acid (AA) and AOE was prepared by adding 6.0g of AA and 6.0g of AOE to 288.0g deionized water with vigorous agitation.

[0083] To a two liter autoclave were added 900g of deionized water, 2.3g of low molecular weight poly(acrylic acid) (BASF CP-10S), and lOg of the AOPD solution. The autoclave was deoxygenated by admission of 60psi nitrogen and venting, repeating this procedure two more times. Agitation was started and the autoclave was heated to 83C and pressurized to 650psi with vinylidene fluoride. A feed of 4.0wt% each potassium persulfate (KPS) was started at 5.0mL/min. Upon start of pressure drop, an additional feed of AA/AOE was started at l.OmL/min and KPS feed reduced to l.OmL/min. and pressure was maintained by additional VDF feed. Feeds were continued in this fashion, increasing AA/AOE feed rate to moderate instantaneous VDF feed demand to maintain a range of 500-l000g/hr. AA/AOE feed was increased in this fashion up to 5.0mL/min. All feeds were continued until a total of 700g of VDF had been fed to the reactor. Monomer feeds were stopped and the pressure was allowed to autogenously decrease for 10 minutes at which point the reactor was vented to atmospheric pressure and cooled to room temperature. Latex was discharged from the reactor and dried in a convection oven overnight.

[0084] Cathode formulation and fabrication: cathode slurry preparation procedure for laboratory scale is described here. PVDF copolymer of the invention is first dissolved in N- methylpyrrolidone (NMP) solvent, typically in 5-l0wt% concentration. Conductive carbon additive, such as SuperP-Li from Timcal, is added to the binder solution, and mixed using a centrifugal planetary mixer, Thinky AR-310, for 3 repeats of l20s at 2000rpm with lmin air cooling in between. Once the conductive carbon is dispersed in the binder solution, active material such as Celcore® NMC622 (Umicore), and small amount of NMP are added to the mixture, and mixed to form a thick and uniform paste, typically 60s at 2000rpm. Then small amount of NMP is added to the paste and mixed at 60s/2000rpm to gradually reduce the slurry solids (in about 1.5% with each NMP addition) and viscosity. This dilution step is repeated multiple time until the slurry viscosity reaches proper level for coating, typically 3,000-l5,000cP @ l/s shear rate. A typical formulation for our laboratory cathode is active material/carbon/PVDF=97/l.5/L5 wt/wt/wt on dry basis.

[0085] The cathode slurry is then cast onto aluminum foil (l5mm thickness) using adjustable doctor blade on an automatic film applicator (Elcometer 4340). The wet casting is then transferred to a convection oven, and dried at 120C for 30min. After drying, the electrode is calendered using a roll mill (IRM, international roll mill), to a final density of 3.2-3.6 g/cm3, with a typical value of 3.4g/cm3. The typical areal mass loading of the dry cathode is 180-220 g/m2.

[0086] Peel strengths for cathodes were obtained via a 180° peel test using ASTM D903 with three modifications. The first modification was that the extension rate used was 50 mm/minute (peel rate of 25 mm/minute). The second modification was that there was no two week conditioning period at a controlled humidity and temperature. Cathodes were tested one day after fabrication. The third modification was that the cathode was bonded to the alignment plate via 3M’s 410M double sided paper tape with the flexible aluminum foil current collector peeled by the testing machine’s grips.

Table 1

*rounded to nearest lOOppm based on NMR analysis sensitivity ppm is measured in weight per weight.